J ~ " ' MM II II II MM 1 1 II MM Ml II I II European Patent Office _ _ _„. © Publication number: 0 3 2 7 4 6 7 B 1 Office europeen des brevets

© E U R O P E A N PATENT S P E C I F I C A T I O N

© Date of publication of patent specification: 08.12.93 © Int. CI.5: A01 N 53/00, //(A01 N53/00 , 5 3 : 0 0 , 4 3 : 3 0 )

© Application number: 89400317.7

@ Date of filing: 03.02.89

© Arthropodicidal compositions.

© Priority: 05.02.88 HU 54088 H-1014 Budapest(HU) Inventor: Szego, Andras, Dr.

@ Date of publication of application: 8, Krudy u. 09.08.89 Bulletin 89/32 H-1088 Budapest(HU)

Inventor: Szekely, Istvan, Dr. © Publication of the grant of the patent: 6, Krajcar u.

08.12.93 Bulletin 93/49 H-2120 Dunakeszl(HU) Inventor: Hidasi, Gyorgy

© Designated Contracting States: 7/a Sarret u. BE CH DE FR GB IT LI LU NL SE H-1142 Budapest(HU)

Inventor: Zoltan, Sandor © References cited: 7/a Sarkozy u.

EP-A- 0 064 803 H-1140 Budapest(HU) WO-A-86/04216 Inventor: Deak, Anik

93, Erzsebet k. u. © Proprietor: CHINOIN Gyogyszer es Vegyeszeti H-1142 Budapest(HU)

Termekek Gyara RT. Inventor: Hegedus, Agnes To utca 1-5 11,Tenkesu. H-1045 Budapest IV(HU) H-1225 Budapest(HU)

Inventor: Bert k, Bela, Dr. @ Inventor: Pap, Laszl , Dr. 44, Jak u.

19, Vadon u. H-1222 Budapest(HU) H-1112 Budapest(HU) Inventor: Sarkozl, Peter, Dr. 19, Varfok u. H-1014 Budapest(HU) Inventor: Somfai, Eva, Dr. 8, Tancsics M. u.

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CO

CM 00

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid (Art. 99(1) European patent convention).

Rank Xerox (UK) Business Services (3. 10/3.6/3.3. 1)

EP 0 327 467 B1

Inventor: Botar, Sandor, Dr. 49, Arany J. U. H-1222 Budapest(HU) Inventor: Gajary, Antal, Dr. 15/a, Boloni Gy. u. H-1021 Budapest(HU) Inventor: Nagy, Lajos 16, Vasarhelyi K. ter H-2000 Szentendre(HU)

0 Representative: Ahner, Francis et al CABINET REGIMBEAU 26, avenue Kleber F-75116 Paris (FR)

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EP 0 327 467 B1

Description

The present invention relates to arthropodicidal compositons containing several pyrethroidal active ingredients. The invention particularly relates to synergistic arthropodicidal compositions containing several pyrethroidal active ingredients which are not toxic to warm-blooded organisms.

The composition, according to the invention, consists of a synergistic mixture of a pyrethroidal active ingredient 1StransR-alpha-cyano-3-phenoxy-benzyl-3-/2,2-dichlorvinyl/-2,2-dimethyl-cyclopropane carbox- ylate of the Formula I

10

15

20

C I

C I

: c - c h

and tetramethrin or trans-tetramethrin of the Formula II

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30

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55

C H 3 x

C H 3 "

C - C H

0 - C H 2 - N

and 1 RtransS-alpha-cyano-3-phenoxy-benzyl-3-(2,2-dichlorvinyl)-2,2-dimethyl-cyclopropane carboxylate I' as a further pyrethroidal substance as well as piperonyl butoxide of the Formula III and additives.

C H 2 O C H 2 C H 2 0 C H 2 C H 2 0 C z > H 9

C H 2 C H 2 C H 3 \ \ .

The compound of the Formula I amounts to 0.1-20% by weight, the compound I' amounts to 0.1-20% by weight, the compound of the Formula II amounts to 0,05-10% by weight and the piperonyl butoxide of the Formula III amounts to 0.1-40 % by weight. The remaining amount up to 100 % consists of additives. The ratio of 1 StransR to 1 RtransS amounts to 0.7-1 .3 : 1 .3-0.7, preferably 1 :1 .

The following abbreviations are used throughout the specification: Alphamethrin

TET =

deltamethrin

trans TET

/S/-alpha-cyano-3-phenoxybenzyl-/1R,3R/-3/2,2-dichlorvinyl/ -2,2-dimethyl- cyclopropane-carboxylate and /R/-alpha-cyano-3-phenoxy-benzyl-/1 S,3S/-3/2,2- dichlorvinyl/-2,2-dimethyl-cyclopropane carboxylate tetramethrin = 3,4,5,6-tetrahydro-phtalimido-methyl/1 RS/-cis-trans-chrysan- themate /S/-alpha-cyano-3-phenoxy-benzyl/1R,3R/-3/2,2,-dibrombinyl/-2,2-dimethyl- cyclopropane carboxylate trans tetramethrin = 3,4,5,6-tetrahydro-phtalimido-methyl/1 RSMrans chrysan-

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EP 0 327 467 B1

themate TRX = transmix = a mixture of 1StransR-alpha-cyano-3-phenoxy-benzyl-3-/2,2-dichlorvinyl/-2,2-

dimethyl cyclopropane carboxylate and 1 RtransS-alpha-cyano-3-phenoxy-benzyl- 3-/2,2-dichlorvinyl/-2,2-dimethyl-cyclopropane carboxylate

5 SF = synergistic factor PBO - piperonyl butoxide

The composition according to the invention may be used in all those locations wherein only such substances may be applied which are substantially not toxic to warm-blooded organisms, such as agricultural and horticultural pests, i.e. pests occurring in preserved food industry and refrigerating industry.

io Various parasitic arthropodal pests cause significant harm in stock breeding. By disquieting the animals the pests cause a reduction of their yield capacity, their gain in weight, they disturb their behaviour and their technology tolerance increasing thereby the number of compulsory slaughtering. Significant yield losses are caused by the store arthropoda as well, and this is worsened by the fact that these crops are already produced /i.e. costs are already involved/ and the protection is needed for the whole provision storing period

is during the utilization of the crops to avoid the presence of substances being harmful for men and animals in provision.

During the protection against diseases propagated by various arthropoda such as malaria, yellow disease, sleeping disease, dysentery, plague, it is important that only such agents may be applied which are not toxic to warm-blooded organisms, are intoxic dermally, do not cause dermal irritation and allergy.

20 As the most widely used insecticides are neuroactive substances /nerve poison/ the function of such nerves is damaged which can be found in both inferior and superior animals /F. Matsumura: Differential toxicities of insecticides and halogenated aromatics, Pergamon Press 1984/. Consequently, the selectivity of most of the compositions is not sufficient.

The compositions according to the invention show an outstanding activity against the following pests: 25 flies such as Hydrotaea irritans, Morellia simplex, M. Hortorum, Haematobla spp., Stomoxys calcitrans,

Musca domestica, M. autumnalis, Glossina app., Simulium spp., Culicoides, Phlebotomus spp., Tabanidae/; fleas such as Xenopsylla spp., Pulex spp., Ctenocephalides app./; bugs such as Cimex spp., Triatoma spp., Rhodnius spp., Triatoma spp./; louses such as Pediculus spp., Phthirius pubis, Damalinia, Haematophinus; ticks resp. mites such as Ixodes, Sporoptes spp., scabiei; mosquitoes such as Anopheles spp., Aedes spp.,

30 Culex spp., Mansonia spp.; cockroaches such as Blattella germanica, Blatta orientalis, Periplaneta ameri- cana, Periplaneta australasie, Supella longipalpa; various store pests such as Tribolium spp., Trogoderma spp., Stegobium spp., Sitophilus spp., Tenebrio spplk, Stagobium paniceum, Sitotroga cerealella, Zaorotes subfasciatus, Rhyzopertha dominica, Ptinus spp., Cryzaephilus surinamensis, 0. mercator, Lasioderma serricorne, Necrobia spp., dermestes spp., Carpopohilus spp., Dryptolestes spp., Mezium spp., Alphitobius

35 diapersinus, A.laevigatus, Callosobruchus spp., Bruchus spp., Anthrenus verbasci, Ephestia spp., Plodia interpunctella, Acaris siro, Tyrophagus putres, T.centiale, T.longinor, Tyrolichus casei; agricultural pests belonging to genera Lepidoptera, Coleoptera, Heteroptera, Homoptera, Hymenoptera, Diptera and Acarifor- mes.

We have now found that IStransR isomer being the least active out of the 4 trans isomers of 40 cypermethrin can be transformed to a synergistic active and stable composition when combined with

1 RtransS isomer, tetramethrin and piperonyl butoxide. Thus the advantages of the very low toxicity against warm-blooded animals can be utilized and outstanding selective arthropodicidal composition may be prepared. The data relating to synergistic compositions are shown in Table 1.

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EP 0 327 467 B1

Table 1

Interaction of transmix isomers and piperonyl butoxide on house fly /Musca domestica/ tested by topical method

isomers and active activity without PBO activity with PBO/1 :2/* ng/fly SF ingredient mixtures resp. LD50M ng/fly

IRtransS 5.78 4.58 1.26 IStransR 571.50 278.62 2.05 TRX 6.70 3.76 1.78 TRX + TET (10:1) 8.02 2.97 2.70 TRX + TET (10:5) 8.41 2.87 2.93

x = calculated to trans cypermethrins

As excipients anionic tensides, such as calcium alkyl aryl sulfonate, calcium dodecyl benzene sulfonate or non-ionic surfactants such as nonyl or dinonyl phenol ethoxylates /EO = 16-20/ are used. The composition may contain further non-ionic components such as tristyryl phenol ethoxylates /ED = 20/ etc.

As filling agent the composition may contain solvents such as xylene, aromatic solvent mixture, aliphatic hydrocarbon mixtures, alkyl benzene, mineral or vegetable oile and solid carriers etc.

The formulation of the composition depends on the method of application. In order to prepare emulsifiable compositions anionic tensides, non-ionic surfactants and other non-ionic components and solvents are preferable admixed to the mixture. As anionic tensides 2 to 5 % by weight of calcium alkyl aryl sulfonate, and as non-ionic surfactant 1 to 2 % by weight of nonyl-, dinonyl phenol ethoxylates /EO = 16-20/ and as further non-ionic components 0.5-2 % by weight of tristyryl phenol ethoxylates (EO = 20/ and as solvent xylene may preferably be used.

A transparent emulsifiable composition may be prepared by using as anionic tenside 2.5-9 % by weight of a calcium salt of alkyl aryl sulfonate, and as non-ionic surfactant 1 .25-3.5 % by weight of nonyl-, dinonyl phenol ethoxylates /EO = 16-20/and as further non-ionic component 0.7-3.5 % by weight of tri-styryl phenol ethoxylates /EO = 20/ and as solvent preferably 5-10 % by weight of xylene, 1-3 % by weight of ethylene glycol and water up to 100 % by weight.

Wettable powders can also be prepared by adding dispersing agents and carriers. According to a preferred feature as dispersing agent 1-2 % by weight of dioctyl sulfosuccinate and 6-8 % by weight of polymerized sodium naphtaline sulfonate and as carrier silicic acid and talc may be used.

Pests to be found on water-sides or other large fields, such as mosquitoes, can be combated by using the composition according to the invention in ULV form by aeroplain or helicopter spraying. Such compositions contain apart from the active ingredient as aliphatic hydrocarbon mixture and mineral or vegetable oil at a ratio of 1:100-1:2 as filling agent. The composition of the invention can be formulated according to other methods as well, such as Hungarian Patent Applications Nos. 3245-87, 3246-87, 4975-87, 4974-87.

The active ingredients may be prepared by methods known per se such HU-PS 152 558 and EPA 86900 830 etc.

Known pyrethroidal combinations are e.g. mixtures of permethrin and decamethrin /EP No 5826/ and mixtures of permethrin and tetramethrin /HU-PS 184 614, DOS 2704 066/. The compositions of the present invention are more efficient than the known compositions and are also active against certain strains which are resistant to said known compositions /See biological Example 3./.

The details of the invention can be illustrated by the following non-limiting Examples.

5o I. Biological Examples

Example 1

Test animal: In laboratory cultivated 3-5 days old female house fly /Musca domestica/ WHO/SRS imagoes. The active ingredient, n-butanol or ethoxy ethanol are dissolved in /cellosolve/ and the solution is applied in 0.22 u\ drops on the dorsal cuticule of the flies moderately narcotized with carbon dioxide. The treated flies are provided with sugar and water ad libitum in plastic glasses and evaluated after 24 hours. The ratio of killed flies is expressed in percentage (mortality %). The LD5o values are calculated from the obtained data by probit analysis.

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EP 0 327 467 B1

10

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20

25

The combinative interaction is given as a ratio of the expected activity /E/ and the measured activity /M/ calculated on the basis of the activity of the components per se. If the measured activity surpasses the expected activity then the activity is syn ergistic and if the two activities are the same then the activity is additive, whereas if the measured activity does not achieve the expected activity then there is an antagonistic activity between the two components.

The expected value can be determined by harmonic average:

E x p e c t e d LD^q j ̂ + g / _ A + B

A + B

LD50A LD50B

The synergistic factor can be expressed as a ratio of the expected and measured values:

SF = E x p e c t e d L D ^ n / k + B /

Measured LD^g /A+B/

wherein SF stands for synergistic factor, A and B stand for the amount of the components /or ratio thereof/ and in the index they relate to the corresponding LD5o values.

The obtained results show the outstanding synergistic activity of the 1:1 mixture of 1 RtransS + 1 StransR 30 /transmix/ isomers next to the different behaviour of the various cypermethrin isomers /See Table 1/.

In case of the piperonylbutoxide which itself is not very active the synergistic activity can be deduced from the decreasing number of the LD5o values. The effect of piperonyl butoxide on the activity of some cypermethrin isomers on house fly /Musca domestica /SRS/ measured by topical method is shown in the following table.

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EP 0 327 467 B1

T a b l e 2

d o s e , a c t i v i t y c h a n g e o f / n g x f l y / per se w i t h PB0X a c t i v i t y

I R e i s S MORTALITY % 0 . 5 0 5 5 0 0 .72 15 20 + 5 1 .03 30 30 0 1 .47 50 65 + 15 2 .10 BO 75 - 5

LD5Q 1 .37 1 . 3 0

I R t r a n s S MORTALITY % 1 .56 10 10 0 2 . 5 9 20 30 + 10 4 . 3 2 40 50 + 10 7 .20 60 65 + 5

1 2 . 0 0 75 85 + 10 LD5Q 5 . 7 8 4 . 5 8

I S t r a n s R MORTALITY h 118 0 . 5 + 5 168 0 15 + 1 5 240 0 35 + 3 5 343 20 70 + 50 490 45 85 + 40 700 60 100 + 40

1000 80 100 + 20 LD5Q 5 7 1 . 5 2 7 8 . 6

l R t r a n s S + I S t r a n s R ( 1 : 1 ) MORTALITY \

1 . 56 0 15 + 1 5 2 . 5 9 10 30 + 20 4 . 3 2 30 55 + 25 7 . 2 0 50 80 + 30

1 2 . 0 0 80 95 + 15 LD5Q 6 . 7 0 3 . 7 6

R a t i o of p y r e t h r o i d e and p i p e r o n y l b u t o x i d e = 1 : 2

Example 2

Mixtures of transmix + tetramethrin of different ratio were tested by applying the above methods with piperonyl butoxide and without. The obtained results (Table 3) indicate a moderate antagonism in case of

55 simple combinations of two components: transmix and transmethrin. Table 4, however, shows an unex- pected synergistic activity of the double combination admixed with piperonyl butoxide, which cannot be explained with any synergistic activity of the two pyrethroides per se and piperonyl butoxide. TET per se is inefficient at the used dose.

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EP 0 327 467 B1

f a b l e 3 Effec t of mixtures of transmix and t e t r a m e t h r i n of v a r i o u s r a t io on house fly (Musca domestica/SRS) measured by t op ica l method

dose / n g x f l y / TRX TET TRX+TET e x p e c t e d ac- c h a n g e o f TRX TET m e a s u r e d a c t i v i t y t i v i t y (%) a c t i v i t y TRX:TET = 10:1 M O R T A L I T Y %

1.7 0 .17 10 0 0 10 - 10 2.4 0 .24 25 0 0 25 - 25 3.4 0 .34 35 0 10 35 - 25 4.8 0 .48 45 0 20 45 - 25 6.9 0 .69 55 0 35 55 - 20 9.8 0 .98 80 0 70 80 - 10

LD50 5 .16 - 8 . 4 9

TRX : TET = 10:5 M O R T A L I T Y % 1.7 0 .82 10 0 0 10 - 10 2.4 1 .18 25 0 0 25 - 25 3.4 1 .68 35 0 10 35 - 25 4.8 2 .40 45 0 25 45 - 20 6.9 3 .43 55 0 35 55 - 20 9.8 4 .90 80 0 65 80 - 15

LD50 5 .16 - 8 . 4 1

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EP 0 327 467 B1

Table 4

T o t a l e f f e c t of p i p e r o n y l b u t o x i d e , t r a n s m i x a n d 5

t e t r a m e t h r i n on house f ly /Musca d o m e s t i c a / S R S /

m e a s u r e d by t o p i c a l m e t h o d

10

dose / n g x f l y " 1 / TRX TET TRX+TET e x p e c t e d c h a n g e o f TRX TET measured e f f e c t e f f e c t (%) e f f e c t

TRX:TET:PBO = 1 0 : 1 : 2 0 M o r t a l i t y h

1.7 0 . 1 7 10 0 15 10 + 5 2.4 0 . 2 4 25 0 35 25 + 10 3.4 0 . 3 4 35 0 60 35 + 25 4 .8 0 . 3 4 45 0 80 45 + 35 6 .9 0 . 6 9 55 0 95 55 + 40 9 .8 0 . 9 8 80 0 100 80 + 20

LD50 5 .16 - 2 . 9 7

T R X : T E T : P B 0 = 1 0 : 5 : 2 0 M o r t a l i t y %

1.7 0 . 8 2 10 0 20 10 + 10 2.4 1 . 1 8 25 0 40 25 + 15 3.4 1 . 6 8 35 0 60 35 + 25 4.8 2 . 4 0 45 0 80 45 + 3 5 6.9 3 . 4 3 55 0 90 55 + 35 9.8 4 . 9 0 80 0 100 80 + 20

LD5Q 5 .16 - 3 . 0

Example 3

40 Test of efficiency on resistant insects

House fly larvae /Musca domestica/NTR/ collected from pigfarm were bred to developed insects. The permethrin's activity was tested by enhanced increase of the LD5o values, whereafter a great heterogenicity was observed, resulting in a levelling out of the dose-effect curve and in the enhanced increase of the LD95.

45 In order to strengthen resistance and to ensure the homogenicity of the population and an appropriate amount of test insects, the collected fly population was subjected to selection pressure for 5 generations at a level of LDGo, by treating 2000 male and 2000 female flies in each generation with the given dosage /LD7o/ topically. The surviving flies gave the parent generation. The culturing was carried out by Sawicki as follows.

50 The insects were examined according to the method given before Example 1. The LD50 values were obtained by probit analysis.

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EP 0 327 467 B1

Table 5

E f f i c i e n c y of t r a n s m i x : t e t r a m e t h r i n c o m b i n a t i o n s on

house f ly /Musca d o m e s t i c a / N T R / t e s t e d by t o p i c a l m e t h o d

a c t i v e i n g r e d i e n t s and m i x t u r e s

LD, p o '

rn / n g x f l y " ' ' ' / r e s i s t a n c e f a c t o r

3 U r- ,n / i n LD 50F .

/LD 50P ,

p e r m e t h r i n 2 8 . 5

t e t r a m e t h r i n 4 5 0

TET+PBO ( 1 : 2 0 ) 3 1 0

t r a n s m i x 8 . 6

t r a n s m i x + T E T ( 1 0 : 1 ) 9 . 5

t r a n s m i x + T E T + P B O 5 . 8 ( 1 0 : 1 : 2 0 )

t r a n s m i x + T E T + P B O 3 . 3 ( 1 0 : 1 : 4 0 )

t r a n s m i x + t r a n s T E T + P B O 4 . 9 ( 1 0 : 1 : 2 0 )

2 9 0 . 7

> 5 0 0 0

1 5 0 0

1 7 . 5

2 1 . 2

7 . 2

7 . 1

5 . 9

1 0 . 2

> 1 1

5 . 2

2 . 2

2 . 2

1 . 2

1 . 3

1 . 2

Pq = p a r e n t g e n e r a t i o n

Fg = o f f s p r i n g g e n e r a t i o n

The results indicate that the effect of transmix + tetramethrin-piperonyl butoxide mixtures on resistant flies is significant.

Example 4

Emulsifiable concentrates prepared according to Examples 3 or 4 were diluted with 200-400-800-1600- 3200-6400 fold water and the obtained emulsions were sprayed with a 2 layer pulverizer in 0.5 ml portions at a pressure of 2 bar into Petri-dishes of a diameter of 9 cm. After drying 3-5 days old female flies /Musca domestica /SRS/ were placed to Petri-dishes /10 to each dish/ in 4 replicates for each dosage. After 60 minutes the knocked down flies were calculated and their ratio was expressed in percents/see Table 6/.

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EP 0 327 467 B1

Table 6

composition dilution

200 400 800 1600 3200 6400

knockdown (%)

Emulsion of formulation Example 4 100 100 75 50 30 10 Emulsion of formulation Example 3 100 100 85 60 35 10 StomosanR 100 80 40 15 0 0

StomosanR = Composition containing 200 g/l of commercially available permethrin

The table shows that the knock-down effect is considerable even at a great dilution. 75

Example 5

Test insects: cockroaches /Blatella germanica/

20 20 male cockroaches obtained from a 1-2 weeks continuous laboratory culture were treated topically in a mild carbon dioxide narcosis with 0.22 u\ n-butanol solution of the test-compounds of a suitable concentration.

3 days after the treatment the insects which were provided ad libitum with water and commercially available dogfood in plastic glasses, were evaluated. The ratio of the killed insects was expressed in

25 percents. The results are shown in Table 7.

Table 7

test components dosage /ngxcockroach V

4.5 9 18 39 78

Mortality (%)

TRX 0 0 35 60 90 TET 0 0 0 0 0 TET + PBO (1:20) 0 0 0 0 0 TRX + TET (10:1) 0 5 30 60 90 TRX + TET + PBO (10:1:20) 15 55 85 100 100

40

Example 6

Test insect: flour beetle (Tribolium confusum)

20 imagoes obtained from a 1-2 weeks continuous laboratory culture were treated for each dosage with 0.22 M.I of n-butanol solution of the tested compounds topically. The treated insects were held in a glass vial sealed with a cotton wool stopper. The percent of the killed insects after 24 hours is shown in Table 8.

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EP 0 327 467 B1

Table 8

test compounds dose /ngxinsect V

0.78 1.56 3.13 6.25 12.5 25 50 100

transmix /TRX/ 0 0 15 25 45 60 70 85 tetramethrin /TET/ 0 0 0 0 0 0 0 0 tetramethrin + PBO (1 :20) 0 0 0 0 0 0 0 0 transmix + PBO (1:2) 0 0 20 40 60 75 90 100 TRX + TET + PBO (10:1:20) 10 35 50 65 80 90 100 100

II. Formulation examples 75

Emulsifiable concentrates (Examples 1-8)

Piperonyl butoxide, calcium salt of alkyl aryl sulfonate, nonyl phenol- and dinonyl phenol ethoxylate and tristyryl phenol ethoxylate are dissolved in 500 ml of xylene at 40 ° C and the pyrethroides are added under

20 stirring and the solution is completed to 1000 ml at 20 °C /See Table 9/. The compositions according to 1 to 8 in Table 9 were tested for stability in CIPAC A and D water at

+ 30 °C in 0.2, 1 and 5 % by volume. The samples were subjected to heat treatment for 14 days at 54 ± 2 °C and at the given temperature

emulsion stability and redispersion tests were carried out in the above CIPAC waters. The 8 samples 25 showed similar behaviour within 10 % standard deviation like the freshly prepared sample.

12

v̂q O f— 1 O VO CD ITS O O ■—1 rH E O

L P i O ^ 0 ^ o o o o rH ^ rH rH CM (—) i— 1 E O

<■ O ^ O ^ LP\ LP* LP, O LPl O '"" 1 rH <j- ,-H . — 1 r— 1 cn e CD 4-> O co o ^ o o o o o o

U r^ i tA O CM CM CM LP, O +-> CM rH c CD .—1 U \ rH C 03 £ O U C ° ■H CM O ^ O LPi O IPi LP, O CD CM CO 1 >— 1 r̂ i O 1 — i cn i— t .□ +-> CO c ■ ■ - 1 3 rH <M O E ■■h E cn co ■— ( o ^ o a o o o o ■— 1 CM <S" rH CM rH it O 3 O E rH LU

CD +-> CD CO -H rH 1 CD CO rH -H rH X CO >, O (-1 rH X CO >> O - H I X JT CD rH cn o +-> rH >< fH JZ ^ CD O _̂ 0) +-> O rH C rH JD C CD CM O rH CD CO CD E -H rH C JT -+-> D (h 0 II CD II Q. 1H CO c .c c rH o c X +-> CD O Q.O >> O On CD -H CD J T U J r H U J t - l + J l H rH E E CLw >,W >, rH i— 1 CD cd q. in co ■—* c +-> co 3 c ■-I e c ( h o in en to cd -O CO CO -H> O C d -H i— 1 CO X L-l CD CO O -H UCO >> i— l l j i— r - o _ 2 : a i — u x

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EP 0 327 467 B1

Transparent solutions

General method

5 Piperonyl butoxide, calcium salt of alkyl aryl sulfonate, alkyl phenol ethoxylates and tristyryl phenol ethoxylate are dissolved in an aromatic solvent mixture of a suitable amount whereafter transmix and tetramethrin are added at 40 °C. The obtained solution is poured into 500 ml of ion exchanged water containing 8 % ethylene glycol and it is completed to 1000 ml at 20 °C with water containing 8 % ethylene glycol /see Table 10, Examples 9-16/.

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EP 0 327 467 B1

5

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30

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O CM O I O LP, o o o rH ■* i— 1 -sT LP, O rH

rH E O

LP, O CM O 1 LP, LP, O O O H H CM r H L P V O L P l O

rH rH E o ^ O r H O LP, 1 O LP, O O

rH 1-1 M3 LP, O rH rH E O f V O r H O LP, 1 O LPiO o i— I i— 1 CM CO -3" LP, O rH

rH E CM O LP, O 1 LP, LP, O O O CD < — 1 LP, O rH LP, MD O O C rH ,_, 0 O rH •rH --" rH = ^ E rH CD O r H O L P \ 0 LP, O LP, O O O m C r H L P v o r H < ^ r ~ o o •H CM rH O +> rH C CO CD -P ^ n c e CO 13 □. O O O CM O O 1 o o o o C O E r H C M C O r H f\ NO CT\ O C CO o CO rH u h-

rH E ON O CM O O LP, O O O O CM <t f"> CM M3 ON O O rH

CD 4-» CD CD CO U U -H rH 1 3 CD CD CO >, rH +-> 4-> ■+-> rH X X CO CO >s O 4̂ -rH 3 rH X _C CO E >. O +-> 1 rH X _C CD rH +-> O cn o -h rH >, c u fn _C CD O CD >̂ CD 4-> r-l (Z > r-t .o c cd a cd c o a i r H O ) E -rH rH C .CJ +■> O CD C 3 t-i o '-n cd ^ q.'-n tw co lo CO C JTJ C O _ C . V j O r H O O C CD -rH O X +-> CD CM CXrH >>CM O U H -H rH CD -H CD -C II rH II II -H <M -rH >, 3 < — 1 E E Q.O >>0 >^0 r-i <—< -H r H CD Q. CO CO T - H L L J C U J - H L I J C 0 3 C 0 - H O rH E C U ><w O w LOW COCO E CD CO .a co co -t-> o c c - H o CO X U CD CO O -H t-l CO f-i e\° 1— L U r - l — Q _ 2 O t— O < CO

The above transparent solutions were examined by the method described for the emulsifiable con- centrates. The stability of the samples before and after the storage was found to be suitable.

15

EP 0 327 467 B1

Example 17/ULV/

20 g of piperonyl butoxide, 10 g of transmix and 1 g of tetramethrin were completely dissolved in 250 ml Solvesso 150 and it is completed to 1000 ml at 20 °C with paraffin oil.

5 Example 18/ULV/

10 g of piperonyl butoxide, 5 g of transmix and 1 g of tetramethrin are dissolved in 250 ml of Solvesso 150 whereafter it is completed with sunflower oil to 1000 ml at 20 °C.

10 Example 19 /WP/

In a two layer pulverizer laboratory fluidization drying equipment on 745 g of silicic acid at 40 ° C, under 2 bar liquid pressure and 3 bar air pressure a solution of 200 ml xylene, 100 g of piperonyl butoxide, 50 g

is of transmix and 5 g of tetrmethrin is pulverized. To the dried powder 20 g of dioctyl sulfosuccinate and 80 g of polymerized sodium salt of alkyl naphtalin sulfonic acid are mixed. The homogeneous powder mixture is ground to a size below 20 micrometer by using an ultraplex mill. Moisturization time: 16 sec. Floatability according to CIPAC: 86 %.

20 Example 20

A solution of 150 ml of xylene, 20 g of piperonyl butoxide, 10 g of transmix and 1 g of tetramethrin is sprayed on 894 g of silicic acid according to Example 19. 15 g of dioctyl sulfosuccinate and 60 g of polymerized sodium alkyl naphtaline sulfonate are added to the dry powder mixture in a homogenizer, and

25 the mixture is ground. Mositurization time of the powder mixture: 12 sec, floatability: 88 %.

Example 21

A solution of 75 ml of xylene, 2 g PBO, 1 g of transmix, and 0.1 g of tetramethrin is sprayed on 996 g 30 of silicic acid by a method given in Example 19. The product can be used without grinding as a dusting

agent.

Example 22

35 A solution of 100 ml of xylene, 10 g of piperonyl butoxide, 5 g of transmix and 0.5 g of tetramethrin is applied to 985 g of silicic acid as given in Example 19. Dusting agent is obtained.

Claims

40 1. A synergistic arthropodical composition causing no damage to warmblooded organisms which consists of a synergistic mixture of

1- as pyrethro'fd component the following active ingredients: a) 0.1 to 20% by weight of 1StransR-alpha-cyano-3-phenoxy-benzyl-3-(2,2-dichlorovinyl)2,2- dimethyl-cyclopropane-carboxylate;

45 b) 0.1 to 20% by weight of 1 RtransS-alpha-cyano-3-phenoxy-benzyl-3-(2,2-dichlorovinyl)2,2- dimethyl-cyclopropane-carboxylate, the weight ratio of 1 StransR to 1 RtransS being between 0.7- 1.3 : 1,3-0,7; c) 0.05 to 10% by weight of 3,4,5,6-tetrahydro-phtamilido-methyl-(1 RS)-cis-trans-chrysanthemate or 3,4,5,6-tetra-hydro-phtamilido-methyl-(1 RS)-trans-chrysanthemate; and

50 2- as synergist component, 0.1 to 40% by weight of piperonyl butoxide; and additives to give 100% by weight.

2. Composition according to claim 1 which comprises as additives 0.01-20 % by weight of excipient and/or colouring agent and/or filling agent in an amount to give 100 % by weight.

55 3. Composition according to claim 2 which comprises 0.01-20 % by weight of excipient, preferably

calcium dodecyl benzene sulfonate as anionic tenside, nonyl-, dinonyl-phenol ethoxylates (EO = 1 -20) as non-ionic surfactants and tristyryl phenol ethoxylate (EO = 20) as a further non-ionic component.

16

EP 0 327 467 B1

4. Composition according to claims 2 ox A which comprises xylene, aromatic solvent mixture, aliphatic hydrocarbon mixture, alkyl benzene, mineral and/or vegetable oil as solvents.

5. Emulsifiable concentrate according to claims 2 to 4 which comprises 2-5 % by weight of calcium alkyl 5 aryl sulfonate as anionic tenside, 1-2 % by weight of nonyl-, dinonyl phenol ethoxylate (EO = 16-20) as

non-ionic surfactant and 0.5-2 % by weight of tristyryl phenol ethoxylate /EO = 20/ as further non-ionic component and preferably xylene as a solvent.

6. Transparent emulsion composition as claimed in claims 2 to 4 which comprises 2.5-9 % by weight of io calcium alkyl aryl sulfonate as anionic tenside, 1.35-3.5 % by weight of nonyl-, dinonyl-phenol

ethoxylates as non-ionic surfactant (EO = 16-20) and 0.7-3.5 % by weight of tristyryl phenol ethoxylates as further non-ionic component (EO = 20) and preferably xylene, 1-3 % by weight of ethylene glycol and water up to 100 % by weight as a solvent.

75 7. Wettable powder composition as claimed in claims 2 to 4 which comprises 1-2 % by weight of dioctyl sulfosuccinate and 6-8 % by weight of polymerized nodium naphtaline sulfonate as dispersing agent and silicic acid, talc as carrier.

8. ULV composition as claimed in claims 2 to 4 which comprises an aliphatic hydrocarbon mixture and 20 mineral and/or vegetable oil at a ratio of 1:100-1:2 as filling agent.

Patentanspruche

1. Synergistisch wirksame arthropodicide Zusammensetzung, die keine Schadigung warmblutiger Orga- 25 nismen hervorruft und aus einem synergistischen Gemisch besteht aus:

1 - den folgenden Wirkstoffen als pyrethroider Komponente: a) 0,1 bis 20 Gew.-% (1S)-trans-(R)-a-Cyano-3-phenoxybenzyl-3-(2,2-dichlorvinyl)-2,2-dimethyl- cyclopropancarboxylat; b) 0,1 bis 20 Gew.-% (1 R)-trans-(S)-a-Cyano-3-phenoxybenzyl-3-(2,2-dichlorvinyl)-2,2-dimethyl-

30 cyclopropancarboxylat; wobei das Gewichtsverhaltnis der (1S)-trans-(R)-Verbindung zur (1R)- trans-(S)-Verbindung 0,7 bis 1 ,3 : 1 ,3 bis. 0,7 betragt; c) 0,05 bis 10 Gew.-% 3,4,5,6-Tetrahydrophthalimidomethyl-(1 RS)-cis-trans-chrysanthemat oder 3,4,5,6-Tetrahydrophthalimidomethyl-(1 RS)-trans-chrysanthemat und

35 2 - 0,1 bis 40 Gew.-% Piperonylbutoxid als synergistischer Komponente und Additiven auf 100 Gew.-%.

2. Zusammensetzung nach Anspruch 1, die als Additive 0,01 bis 20 Gew.-% Excipientien und/oder Farbemittel und/oder Fullstoffe in einer Menge auf 100 Gew.-% enthalt.

40 3. Zusammensetzung nach Anspruch 2, die 0,01 bis 20 Gew.-% Excipientien, vorzugsweise Calciumdode-

cylbenzolsulfonat als anionisches Tensid, Nonyl- oder Dinonylphenolethoxylate (EO = 1 bis 20) als nichtionische grenzflachenaktive Mittel und Tristyrylphenolethoxylat (EO = 20) als weitere nichtionische Komponente enthalt.

45 4. Zusammensetzung nach Anspruch 2 oder 4, die als Losungsmittel Xylol, ein aromatisches Losungsmit-

telgemisch, ein Gemisch aus aliphatischen Kohlenwasserstoffen, Alkylbenzol, Mineralol und/oder Pflan- zenol enthalt.

50 5. Emulgierbares Konzentrat nach den Anspruchen 2 bis 4, das 2 bis 5 Gew.-% Calciumalkylarylsulfonat als anionisches Tensid, 1 bis 2 Gew.-% Nonyl- oder Dinonylphenolethoxylat (EO = 16 bis 20) als nichtionische grenzflachenaktive Mittel und 0,5 bis 2 Gew.-% Tristyrylphenolethoxylat (EO = 20) als weitere nichtionische Komponente und vorzugsweise Xylol als Losungsmittel enthalt.

55 6. Transparente Emulsionszusammensetzung nach den Anspruchen 2 bis 4, die 2,5 bis 9 Gew.-% Calciumalkylarylsulfonat als anionisches Tensid, 1,35 bis 3,5 Gew.-% Nonyl-, Dinonylphenolethoxylate (EO = 16 bis 20) als nichtionische grenzflachenaktive Mittel und 0,7 bis. 3,5 Gew.-% Tristyrylphenolet- hoxylate (EO = 20) als weitere nichtionische Komponente und vorzugsweise Xylol, 1 bis 3 Gew.-%

17

EP 0 327 467 B1

Ethylenglycol sowie Wasser als. Losungsmittel in einer Menge auf 100 Gew.-% enthalt.

7. Zusammensetzung nach den Anspruchen 2 bis 4 in Form eines benetzbaren Pulvers, die 1 bis 2 Gew.- % Dioctylsulfosuccinat und 6 bis 8 Gew.-% polymerisiertes Natriumnaphthalinsulfonat als Dispergier-

5 mittel sowie Kieselsaure oder Talk als Trager enthalt.

8. ULV-Zusammensetzung nach den Anspruchen 2 bis 4, die als Fullstoff ein aliphatisches Kohlenwasser- stoffgemisch und Mineralol und/oder Pflanzenol im Verhaltnis 1:100 bis 1:2 enthalt.

w Revendicatlons

1. Composition arthropodicide synergique qui n'est pas nocive pour les organismes a sang chaud et qui comprend un melange synergique de :

1 . a titre de composant pyrethroide, les ingredients actifs suivants : is a) de 0,1 a 20% en poids de carboxylate de 1StransR-alpha-cyano-3-phenoxy-benzyl-3-(2,2-

dichlorovinyl) 2,2-dimethylcyclopropane ; b) de 0,1 a 20% en poids de carboxylate de 1 RtransS-alpha-cyano-3-phenoxy-benzyl-3-(2,2- dichlorovinyl) 2,2-dimethylcyclopropane, le rapport ponderal du compose IStransR au compose 1 RtransS etant compris entre 0,7-1 ,3/1 ,3-0,7 ;

20 c) de 0,05 a 10% en poids de 3,4,5,6-tetrahydro-phtalimido-methyl-(1 RS)-cis-trans-chrysanthema- te ou 3,4,5,6-tetrahydro-phtalimido-methyl-(1 RS)-trans-chrysanthemate; et

2. a titre de composant synergique, de 0,1 a 40% en poids de butylate de piperonyle ; et des additifs q.s.p 100% en poids.

25 2. Composition selon la revendication 1, qui comprend, a titre d'additif, de 0,01 a 20% en poids d'un excipient et/ou d'un agent colorant et/ou d'une charge en une quantite permettant d'obtenir 100% en poids.

3. Composition selon la revendication 2, qui comprend de 0,01 a 20% en poids d'un excipient, de 30 preference le dodecylbenzenesulfonate de calcium a titre d'agent tensioactif anionique, des nonyl- , di-

nonyl-phenol- ethoxylats (OE = 1 a 20) a titre de tensioactif non ionique et un ethoxylat de tristyryl- phenol (OE = 20) a titre d'un autre composant non ionique.

4. Composition selon les revendications 2 ou 3, qui comprend du xylene, un melange solvant aromatique, 35 un melange hydrocarbone aliphatique, un alkylbenzene, une huile minerale et/ou vegetale a titre de

solvants.

5. Concentre emulsifiable selon les revendications 2 a 4, qui comprend de 2 a 5% en poids d'alkylarylsul- fonate de calcium a titre de tensioactif anionique, de 1 a 2% en poids de nonyl-, di-nonyl-phenol-

40 ethoxylats (OE = 16 a 20) a titre de tensioactif non ionique et de 0,5 a 2% en poids d'ethoxylat de tristyrylphenol (OE = 20) a titre d'un autre composant non ionique et, de preference, du xylene comme solvant.

6. Composition d'emulsion transparente selon les revendications 2 a 4, qui comprend de 2,5 a 9% en 45 poids d'alkylarylsulfonate de calcium a titre de tensioactif anionique, de 1 ,35 a 3,5% en poids de nonyl-

, di-nonyl-phenol- ethoxylats a titre de tensioactif non ionique (OE= 16 a 20) et de 0,7 a 3,5% en poids d'ethoxylats de tristyryl-phenol a titre d'un autre composant non ionique (OE = 20) et, de preference, du xylene, 1 a 3% en poids d'ethylene-glycol et de I'eau q.s.p 100% en poids a titre de solvant.

50 7. Composition de poudre mouillable selon les revendications 2 a 4, qui comprend de 1 a 2% en poids de dioctylsulfosuccinate et de 6 a 8% en poids d'un naphtalenesulfonate de sodium polymerise a titre d'agent dispersant et d'acide silicique et de talc comme vehicule.

8. Composition ULV selon les revendications 2 a 4, qui comprend un melange d'hydrocarbure aliphatique 55 et d'huile minerale et/ou vegetale en un rapport de 1:100 a 1:2 a titre de charge.

18