CA2082533A1

CA2082533A1 - Shaped articles which contain active compounds and are based on elastomeric styrene/butylene block copolymers which can be processed as thermoplastics, processes for their production and their use for control of pests

Info

Publication number: CA2082533A1
Application number: CA002082533A
Authority: CA
Inventors: Heinz-Dieter Brandt; Rolf Dhein; Herbert Hugl; Doris Hackemuller; Wilhelm Stendel
Original assignee: Individual
Current assignee: Bayer AG
Priority date: 1991-11-13
Filing date: 1992-11-10
Publication date: 1993-05-14
Also published as: NO924173D0; AU2825792A; NO303761B1; CN1072692A; PL171240B1; MX9206330A; DE4137272A1; TR26341A; EP0542078A1; NO924173L; JPH05222265A; AU662180B2; HUT64092A; CZ337992A3; IL103700A0; NZ245084A; FI925127A0; PL296588A1; IL103700A; ZA928714B

Abstract

Shaped articles which contain active compounds and are based on elastomeric styrene/butylene block copolymers which can be processed as thermoplastics, processes for their production and their use for control of pests A b s t r a c t The present invention relates to shaped articles which contain active compounds and are characterised in that they comprise, as carriers, thermoplastic elastomeric styrene/butylene block copolymers as well as customary additives if appropriate, and to processes for their production and to their use for control of pests in animals.

Le A 28 735

Description

2 ~ 3 The present invention relate~ to new shaped articles which contain active compounds and are based on elasto-meric styrene/butylene block copolymers which can be processed a~ thermoplastic~, their production and their use for control of pests, in particular in stock and domestic animals.

Shaped articles which comprise active compounds for controlling pests are known. They are bdsed on the slow relea e of active compounds from a carrier matrix of plastics which contains active compounds (compare, for example, Aries et al US P 3 814 061, Greenberg US-P 3 918 407, Miller et al US-P 3 944 662, Millionis et al US-P 4 041 151, Pa~arela US-P 4 145 409, Greenberg and Cloud US-P 4 158 051, v. Bittera et al US-P 4 225 578. McDaniel et al EP-OS O 052 411, Grubb et al US-P 3 852 416 and Pearce US-P 4 536 388).

The carrier employed practically almost exclusively for known 3haped articles is PVC. Although other carriers are mentioned in the literature, as yet they have not found acceptance in practice. Thus, US-P 4 195 075 mentions, inter alia, that thermoplastic elastomer~ are also possible as carrier polymers for ear marks. However, thi~
citation also de~cribes exclusively examples using pla~ticiser-containing PVC a~ the carrier polymer.

This .;.8 al~o not surprising~ PVC i~ inexpensive and Le A 28 735 - 1 -~;...~. ~3 readily accessible. It i~ al80 miscible with other substance~, in particular plasticisers, within wide limits. These plasticisers in PVC bodies containing active compound~ have the function of keeping the active compound dissolved in the carrier and of transporting it 810wly to the surface of the body. At the surface, the active compound evaporates or i8 rubbed off from the ~urface, together with the pla~ticiser. The interaction of the three components PVC carrier, plasticiser and active compound determines whether and to what extent the shaped article can be employed in practice.

If one component of the overall system is changed, it can no longer be predicted whether the system still acts in practice. This applies in particular if the plasticiser, which indeed has a key function in transportation of the active compound, is changed or omitted.

For various rea30ns, it i8 desirable to replace PVC as the carrier material. It is also advantageous to dispense partly or completely with the use of pla~tici6ers. It was therefore a matter of discovering an active compound/
shaped article system in which PVC, as the carrier material, and plasticiser can be dispensed with and which nevertheless has a good action in practice.

Thermopla~tic elastomers are materials which comprise elastomeric phases either mixed physically or bonded chemically in polymers which can be processed as thermoplastic~. A distinction iB made between polyblends, Le A 28 735 - 2 -2~r~

in which the ela~tomeric phases are pre~ent in physically mixed-in form, and block polymers, in which the elasto-meric phases are a constituent of the polymeric matrix.
Hard and soft region~ are pre~ent ~ide by ~ide as a result of the build-up of the thermopla tic elastomers.
The hard regions form a crystalline network structure or a continuous phase, the interstices of which are filled by elastomeric ~egments. On the basis of this build-up, these materials have rubber-like propertie~.

A di~tinction may be made between 5 main groups of thermoplastic elastomerss 1. Copolyesters 2. Polyether block amide~ tPEBA) 3. Thermoplastic polyurethanes (TPU) ~5 4. Thermoplastic polyolefins (TPO) 5. Styrene block copolymers These 5 main groups show similar macroscopic physical properties, coupled with a completely different chemical build-up. In ~pite of these macroscopically similar properties, these main groups behave completely dif-ferently in respect of mixing in and release of active compounds.

The use of thermopla~tic ela~tomers based on copolymers as carriers for active compounds is known. The u~e of styrene/butadiene block copolymers as carriers is de~cri-bed in EP-OS ~European Published Specification) 338 821.

Le A 28 735 - 3 -2~ r~3 The use of polyurethane/polydisiloxane copolymers as carriers is described in EP-OS (European Published Specification~ 338 732.

The present invention relates to 1. Shaped article~ which contain active compounds, characterised in that they compri~e, as csrriers, thermoplastic elastomers based on styrene/butylene block copolymers, as well as customary additives if appropriate.
0 2. Processes for the production of shaped articles ~ontaining active compounds, characteri~ed in that thermoplastic elastomers based on styrene/butylene block copolymers are mixed with active compounds and if appropriate customary additives, and the mixture is processed in the cu~tomary manner.

It was surprising that active compounds also arrive at the polymer surface from the polymer matrix from thermoplastic elastomers based on styrene and butylene without addition of plasticisers, since thiq capacity i8 limited to only a very few polymers. If only one com-ponent of the overall system is changed, the effects are unpredictable. Thermoplastic elastomers based on ther-moplastic olefins (TPO) or thermoplastic polyurethanes, for example, are not capable of allowing active compounds to migrate to the ~urface.

Le A 28 735 - 4 -2t`&~

The styrene~butylene block copolymers which can be used according to the invention consist of a polyethylene-butylene rubber central block with a polystyrene end block linked chemically to both end~. The polystyrene content is les~ than 30%. The polystyrene end blocks are distributed uniformly in the ethylene rubber matrix as spherical polystyrene domains.

Proces~es for the synthesis of suitable styrene block copolymer~ are known, for example, from US-P 3 485 787, 4 006 116 and 4 039 629.

Suitable ~tyrene/butylene block copolymers are obtain-able, for example, under the commercial names ~Kraton G
and ~Elexar from Shell Chemie GmbH and ~Thermolast-K-Compounds from Xraiburg.

Active compounds which may be mentioned for the shaped articles according to the invention are, preferably, insecticides, in particular parasiticides, for use on animals. The insecticides include phosphoru~-containing compounds, such as phosphoric or pho~phonic acid esters, naturally occurring and synthetic pyrethroids, carbam-ates, amidines, juvenile hormones and juvenoid synthetic active compounds.

The phosphoric or phoaphoric acid esters include:

0-ethyl 0-(8-quinolyl) phenyl-thiophosphate (quintiofos), Le A 28 735 - 5 -0,0-diethyl,0-(3-chloro-4-methyl-7-coumarinyl) thiopho~-phate (coumaphos), 0.0-diethyl 0-phenylglyoxylonitrile oxime thiophosphate (phoxim), 0,0-diethyl 0-cyanochlorobenzaldoxime thiophosphate (chlorphoxim), 0.0-diethyl 0-(4-bromo-2,5-dichlorophenyl) phosphoro-thionate (bromopho~-ethyl), 0,0,0',0'-tetraethyl-S,S'-methylene di(pho~phorodi-thionate) (ethion), 2,3-p-dioxanedithiol-S,S-bis(0,0-diethyl phosphorodi-thionate, 2-Chloro-1-(2,4-dichlorophenyl)-vinyl diethyl phosphate (chlorfenvinphos), and 0,0-dimethyl 0-(3-methyl-4-methylthiophenyl) thionophos-phate (fenthion).

The carbamates include:

2-isopropoxyphenyl methylcarbamate (propoxur) and l-naphthyl N-methylcarbamate (carbaryl).

Le A 28 735 - 6 -2 ~ . ~D .. -i ~ J ~3 The Yynthetic pyrethroids include compounds of the formula I

`>< R3 - COO-cH- ~ ~ ~ formula I

in which R1 and R2 represent halogen, optionally halogen-~ubsti-tuted alkyl or optionally halogen-substituted phenyl, R3 represents hydrogen or CN, R4 representq hydrogen or halogen and Rs represent~ hydrogen or halogen, Preferred synthetic pyrethroid~ are those of the formula I in which Rl repre~ent~ halogen, in particular fluorine, chlorine or bxomine, lS R2 represent~ halogen, in particular fluo.rine, chlorine, bromine, trihalogenomethyl, phenyl or chlorophenyl, Le A 28 735 - 7 -~ J3 R3 repre~ents hydrogen or CN, R4 represents hydrogen or fluorine and R5 represents hydrogen.

Particularly preferred synthetic pyrethroid~ are those of the formula I in which R1 represents chlorine, R2 represents chlorine, trifluoromethyl or p-chlorophenyl, R3 represents CN, R4 repre~ent~ hydrogen or fluorine and R5 represents hydrogen.

Compounds of the formula I which may be mentioned in particular are those in which R1 represents chlorine, RZ represents chlorine or p-chlorophenyl, R3 represents CN, Le A 28 735 - 8 -2~:&~-;~-3 R4 repre~ents f luorine in the 4 -position and R5 represents hydrogen.

Compounds which may be mentioned specifically are:

cyano-4-f luoro-3-phenoxy ) -benzyl 3- [ 2- ( 4-chloro-S phenyl ) -2-chlorovinyl ] -2, 2-d~methyl-cyclopropanecarboxyl-ate ( f lumethrin ), ~-cyano ( 4 -f luoro- 3 -phenoxy ) -benzyl 2, 2 -dimethyl- 3- ( 2, 2 -dichlorovinyl ) -cyclopropanecarboxylate ( cyf luthrin ) and its enantiomers and stereomers, ~-cyano-3,-phenoxybenzyl (+)-cis,trans-3-(2,2-dibromo-vinyl ) -2, 2~dimethylcyclopropanecarboxylate ( deltamethrin ), ~-cyano-3-phenoxybenzyl 2, 2-dimethyl-3- ( 2, 2-dichlorovinyl ) -cyclopropanecarboxylate ( cypermethrin ), 3-phenoxybenzyl ( ~ ) -ci3, trans-3- ( 2, 2-dichlorovinyl ) -2, 2-dimethylcyclopropanecarboxylate ( permethrin ), -cyano- 3-phenoxy-benzyl ~ - ( p-Cl-phenyl ) -i~ovalerate ( f envalerate ) and 2 -cyano- 3 -phenoxybenzyl 2 - ( 2 -chloro-~ -trif luoro-p-2 0 toluidino ) - 3-methylbutyrate ( f luval inate ) .

Le A 28 735 - 9 -.. ~3 The amidine include:

3-methyl-2-[2,4-dimethyl-phenylimino]-thiazoline, 2-(4-chloro-2-methylphenylimino)-3-methylthiazolidine, 2-(4-chloro-2-methylphenylimino)-3-(isobutyl-1-enyl)-thiazolidine and 1,5-bis-(2,4-dimethylphenyl)-3-methyl-1,3,5-triazapenta-1,4-diene (amitraz).

The juvenile hormones or ~ubstance~ like juvenile hor-mones include ~ubstituted diaryl ethers, benzoylureas and triazine derivatives. The juvenile hormones and substan-ces like juvenile hormones include, in particular, com-pounds of the following formulae:

,~o~ ~f ~~. ,, H

~ CH 3 i 50-H7C3 CH3 CH3 ~io~

Le_A 28 735 - 10 -Z~ ~r.~3 H3C C~

CH3 CH3 C~3 1I CH3 CH30~ --~--' ol ~3C CH3 H5 C 2><~

H3C~<~

H ~C OCH3 The ~ub~tituted diaryl ether~ include, in particular, Le A 28 735 ~ub~tituted alkoxydiphenyl ethers or -diphenylmethanes of the general formula I

R1 ~ ~ Y-(CH)n-(CH)m-X-Het (I) wherein R1 represents hydrogen, halogen, alkyl, alkoxy, alkyl-thio, halogenoalkyl, halogenoalkoxy, halogenoalkyl-thio, dioxyalkylene, dioxyhalogenoalkylene, CN, NO2, alkenyl, alkinyl, alkoxyalkyl, alkoxyalkoxy or hydroxyalkoxy, R2 represent~ the radicals mentioned for R1, R3 represent~ the radicals mentioned for R1, R4 represent~ hydrogen, alkyl, halogenoalkyl or halogen, R5 representQ the radicals mentioned for R4, S Het represent~ optionally substituted heteroaryl, which is not bonded to the rest of the radical via the hetero atom, Le A 28 735 - 12 -2~

X and Y independently of one another represent -O- or -S-Z represents -O-, -S-, -CH2-, -C~CH3- or -C(~2 ) 2- and m and n independently of one another represent 0, 1, 2 or 3, but their sum i8 equal to or greater than 2.

Particularly preferred compounds of the formula I are tho3e in which R1 represents hydrogen, methyl, trifluoromethyl, methoxy, trifluoromethoxy, chlorine or fluorine R2 represents hydrogen, R3 represents hydrogen, fluorine, chlorine or methyl, R4 represents hydrogen or methyl/

R5 represent~ methyl, ethyl, trifluoromethyl or hydrogen, Het represents pyridyl or pyridazinyl, which are option-ally ~ubstituted by fluorine, chlorine, methyl, NO2, methoxy or methylmercapto, X repre~ents O, Le A 28 735 - 13 -Y represents 0, Z repre~ent~ 0, CH2 or -C(CH332-, m represent3 1 and n represents 1.
The following compound may be mentioned specifically:

R1 ~ Z ~ ~ o_CH2-CH-0 ~ ~

Rl R3 R5 R6 z H H CH3 2-Cl O

H H H H O

H H CH3 H C~CH3)2 Le A 28 735 - 14 -~$~~

- C H 2 - C H - O--< ~

R 1 R3 R5 R6 z -( CH2 ) 3-0-Het.
Rl R3 Rl R3 z He~

H H O ~ ~>
r-~>
H H O

H H O
N----N

Le A 28 735 - 15 -2~ " 3 The benzoylureas include compounds of the formula (V):

~ o-NH-CONH

wherein R1 repre~ents halogen, R2 represents hydrogen or halogen, R3 represent~ hydrosen, halogen or Cl~-alkyl and R4 repre ents halogen, 1-5-halogeno-Cl4-alkyl, C14-alkoxy, 1-5-halogeno-Cl4-alkoxy, Cl4-alkylthio, 1-5-halogeno-Cl4-alkylthio, phenoxy or pyridyloxy, which can optionally be substituted by halogen, Cl4-alkyl, 1-5-halogeno-Cl4-alkyl, Cl4-alkoxy, 1-5-halogeno-Cl4-alkoxy, C,4-alkylthio or 1-5-halogeno-Cl-C4-alkylthio.

The following compounds may be mentioned in particular:

Rl NHCONH ~ ~ R4 Le A 28 735 - 16 -;~ ~; " 3 ~___ _ ___ _____ __ _______ Cl Cl CF3 E~ C 1 OCF3 F F O~

F F O <~CF3 F F O~ ~C F 3 The triazine~ include compounds of the fonnula (VI ) NH-R
NlN
(VI ) ~ N ~

Le A 28 735 - 17 -2 ~ b '~_ 3 wherein Rl represents cyclopropyl or isopropyl;

R2 denotes hydrogen, halogen, C1-Cl2-alkylcarbonyl, cyclopropylcarbonyl, Cl~Cl2-alklcarbamoyl, Cl-Cl2-alkylthiocarbamoyl or C2-C6-alkenylcarbamoyl; and R3 represents hydrogen, C1-C~2-alkyl, cyclopropyl, C2-C6-alkenyl, C1-C~2-alkylcarbonyl, cyclopropylcarbonyl, C1-C12-alkylcarbamoyl, C1-C12-alkylthiocarbamoyl or C2-C6-alkenylcarbamoyl, and acid addition salts thereof which are non-toxic to warm-blooded animals.

Compounds which may be mentioned in particular are:

____ ___ _ _ _ _ _ __ _ _ _ _ _ __ _ _ __ _ __ _ Cyclopropyl H H
Cyclopropyl H CH3 Cyclopropyl H C~H5 Cyclopropyl H C3H7-n Le A 28 735 - 18 -2~

( Continuation ) Rl R2 R3 __ __ ___ ___________________________ Cyclopropyl H C~H9-n Cyclopropyl H C~H11-n Cyclopropyl H C6H13-n Cyclopropyl H C7H15 n Cyclopropyl H CBH17-n Cyclopropyl H C12H25-n Cyclopropyl H CH2-C4H9-~
Cyclopropyl H CH2cHtcH3)c2Hs Cyclopropyl H CH2CH=CH2 Cyclopropyl Cl C2H5 Cyclopropyl Cl C6H13 n Cyclopropyl Cl C8H17-n Cyclopropyl Cl C12H25-n Cyclopropyl H Cyclopropyl Cyclopropyl H COCH3 Cyclopropyl H COCH3'HCl Cyclopropyl H COC2H5'HCl Cyclopropyl H COC2H5 Cyclopropyl H COC3H7 n Cyclopropyl H COC3H7-i Cyclopropyl H COC4Hg-~'HC
Cyclopropyl H COC4H9-n Cyclopropyl H CC6H13-n Cyclopropyl H COCl1-H23-n Cyclopropyl COCH3 COC2H5 Cyclopropyl COC~H7-n COC6H13-n Cyclopropyl COCH3 CC3H7~n Le A 2B 735 - 19 -zr. ~ r~ ~
(Continuation) __ _____ _ ____ _ __ _ _ __ _ ___ ___ ____ _ _________ Cycl~propyl COC2H5 COC~H7-n Cy~lopropyl H COCyclopropyl Cyclopropyl COCyl~lopropyl COCyclopropyl Cyclopropyl COCH3 COCH3 Isopropyl H H
I 50propyl H COCH3 I s~propyl H COC3H7 n Cy lopropyl H CONHCH3 Cyclopropyl H CONHC3H7-i Cyclopropyl CONHCH3 CONHCH3 Cyclopropyl H CSNHCH3 Cyclopr~pyl H CONHCH2CH=CH2 Cyclopropyl CONHCH2CH=CH2 CONHCH2CH=CH2 Cyclopropyl CSNHCH3 CSNHCH3 ~he active compounds having the comnon name~ propoxur, cyfluthrin, flumethrin, pyriproxyfen, methoprene, Diazinon, amitraz and fenthion may be singled out in particular.

The active compounds can be pre~ent in the shaped articles by them~elve~ or as a mixture with one another.

The active compounds are present in the shaped articles in concentration~ of 0.1 - 20 % by weight, preferably of between 1 and 10 % by weight.

~he shaped articles according to the invention can furthermore comprise the additivea customary for plAs-tics. Cu~tomary additivea are, for example, pigment~, Le A 28 735 - 20 -2~?. ~;; 3 stabilisers, flow a~ents, lubricants and mould release agents.

Bxamples of customary additives are:

1. Antioxidants 1.1 A kylated monophenol~, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethyl-phenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-i-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2-(~-methyl-cyclohexyl)-4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol and 2,4,6-tricyclohexyl-phenol, 2,6-di-tert-butyl-4-methoxymethylphenol.

1.2 Alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydro-lS quinone, 2,5-di-tert-amyl-hydroquinone and 2,6-diphenyl-4-octadecyloxyphenyl.

1.3 ~ydroxylated thiodiphenyl ethers, for example 2,2'-thio-bis-(6-tert-butyl-4-methylphenol), 2,2'-thio-bis-(4-octylphenol), 4,4'-thio-bis-(6-tert-butyl-3-methylphenol) and 4,4'-thio-bis-(6-tert-butyl-2-methylphenol).

1.4 Alkylidene-bisphe~ol~, for example 2,2'-methylene-bis-(6-tert-butyl-4-methylph~nol), 2,2'-methylene-bis- ( 6-tert-butyl-4-ethylphenol ), Le A 28 735 - 21 -2~;~.~'?3 2,2'-methylene-bis-(4-methyl-6(~-methylcyclohexyl)-phenol, 2,2'-methylene-bis-(4-methyl-6-cyclohexyl-phenol), 2,2'-methylene-bi~-(6-nonyl-4-methyl phenol), 2,2'-methylene-bis-(4,6-di-tert-butyl-phenol)~ 2,2'-ethylidene-bis~4,6-di tert-butyl-phenol), 2,2'-ethylidene-bis-(6-tert-butyl-4-iso-butylphenol), 2,2'-methylene-bis-[6-(~-methyl-benzyl)-4-nonylphenol~, 2,2'-methylene-bis-[6-(~
dimethylbenzyl)-4-nonylphenol], 4,4~-methylene-bi~-(2,6-di-tert-butylphenol), 4,4~-methylene-bic-(6-tert-butyl-2 methylphenol), 1,1-bi~-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane, 2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1~1,3-tri~-(5-tert butyl-4-hydroxy-2-methylphenyl)-butane, 1,1-bis-(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate], di-(3-tert-butyl-4-hydroxy-5-methyl-phenyl)-dicyclepentadiene and di-~2-(3~-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methyl-phenyl] terephthalate.

1.5 Benzyl compounds, for example 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, di-(3,5-di-tert-butyl-4-hydroxybenzyl) ~ulphide, i800ctyl 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetate, his-(4-tert-butyl-3-hydroxy-2,6-dimethyl-benzyl) dithiol-terephthalate, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) i~ocyanurate, 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) Le A 28 735 - 22 -2 ~ . ~ ~ 3 isocyanurate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzyl-pho~phonate and 3, 5-di-tert-butyl-4 hydroxybenzyl-pho~phonic acid monoethyl ester calcium salt.

1. 6 Acylaminophenol~, for example 4-hydroxy-lauric acid anilide, 4-hydroxystearic aeid anilide, 2,4-bi~-octylmerc:apto-6- ( 3, 5-di-tert-butyl-4-hydroxyanil-ino)-s-triazinc and octyl N-(3,5-di-tert butyl-4-hydroxyphenyl ) -carbamate .

1. 7 Ester~ of _ ~- ( 3J 5-di-tert-bu ~4-hydroxyphenyl ) -pro~2ionic acid with mono- or polyhydric alcohols, such a~, f or example, methanol, octadecanol, 1, 6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaeryth-ritol, tris-hydroxyethyl isocyanurate and di-hydroxyethyl-oxalic acid diamide.

1. 8 Esters of ~- ( 5-tert-butyl-4-hydroxy-3-methylphenyl ) -pro~ionic acid with mono- or polyhydric alcohols, such a~, f or example, with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-hydroxyethyl isocyanurate and di-hydroxyethyl-oxyalic acid diamide.

1. 9 Amides of_ ~- ( 3, 5-di-tert-butyl-4-hydroxypheru~
ProPionic aca,d, auch a~, for ex~lmple, N,N'-di-(3,5-di-tert-butl-4-hydroxyphenylpropionyl ) -Le A 28 735 - 23 -2~ 3 hexamethylenediamine, ~,N'-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine and N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropion-yl)- hydrazine.

2. W absorbers and liqht ~tabilisers 2.1 2-(2'-Hydroxyphenyl)-benzotriazoles, such as, for example, the S~-methyl, 3~,5'-di-tert-butyl, S'-tert-butyl,5'-(1,1,3,3-tetramethylbutyl),5-chloro-3',5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'-methyl, 3~-sec-butyl-5~-tert-butyl, 4~-octoxy, 3',5'-di-tert-amyl and 3',5'-bis-(~,~-dimethyl-benzyl) derivative.

2.2 2-HYdroxybenzophenones, such a , for example, the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyl-oxy, 4-benzyloxy, 4,2',4'-trihydoxy and 2'-hydroxy-4,4'-dimethoxy derivative.

2.3 E _ rs of optionally substituted benzoic acids, such as, for example, 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenz-oylresorcinol, bis-(4-tert-butylbenzoyl)-re~orcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2.4 Acrylate~, such as, for example, ethyl or i~ooctyl ~-cyano-~,~-diphenylacrylate,methyl~-carbomethoxy-Le A 28 735 - 24 -2 ~ d ~ ~3 cinnamate, methyl or butyl ~-cyano-~-methyl-p-methoxy-cinnamate, methyl ~-carbomethoxy-p-methoxy-cinnamate and N-(~-carbomethoxy-~-cyanovinyl)-2-methyl-indoline.

2.5 Nickel compounds, such ~5, for example, nickel complexes of 2,2'-thio-bis-[4-(1,1,3,3-tetramethyl-butyl)-phenol]~ such as the 1:1 or 1:2 complex, optionally with additional ligands, such as n-butylamune, triethanolamine or N-cyclohexyl-dieth-anolamine, nickel dibutyl-dithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzyl-pho~phonic acid monoalkyl esters, such as of the methyl or ethyl ester, nickel complexes of ketoximes, such a~ 2-hydroxy-4-methyl-phenyl undecyl ketone oxime, and nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, op~ionally with additional ligands.

2.6 Sterically hindered amines, such aY, for example, bis-(2,2,6,6-tetramethylpiperidyl) sebacate, bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate, bis-(1,2,2,6,6-pentamethylpiperidyl) n-butyl-3,5-di-tert-butyl--4-hydroxybenzyl-malonate, the condensa-tion product of l-hydroxyethyl-2,2j6,6-tetr~methyl-4-hydroxypiperidine and ~uccinic acid, the condensa-tion product of N,N'-(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris-(2,2,6,6-tetramethyl-4-piperidyl) nitrotriacetate, Le A 28 735 - 25 -2~&.~4~3 tetraki~o(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylic acid and 1,1'-(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone).

2.7 Oxalic acid diamides, ~uch a, for example, 4,4'-di-octyloxy-oxanilide, 2,2'odi-octyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N,N'-bis-(3-dimethyl-aminopropyl)-oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxanilide and it~ mixture with 2-ethoxy-2~-ethyl-5,4~-di-tert-butyl-oxanilide and mixture~ of o- and p-methoxy- and of o- and p-ethoxy-disubstituted oxanilide~.

3. Metal deactivators, such a3, for example, N,N'-diphenyloxalic acid diamide, N-salicylal-N~-salicyl-oylhydrazine, N,N~-bis-(salicyloylhydrazine, N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine, 3-salicyloylamino-1,2,4-triazole and bis-benzylidene-oxalic acid dihydrazide.

4. Pho~phites and pho~phonites, such as, for example, triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl pho~phites, tri-(nonylphenyl) phos-phite, tri:Lauryl phosphite, trioctadecyl phosphite, di~tearyl pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)-phosphite, diisodecylpentaeryth-ritol diphosphite, di-(2,4-di-tert-butylphenyl)-pentaerythritol diphosphite, tristearyl-~orbitol triphosphite, tetr~lkis-~2,4-di-tert-butylphenyl)-Le A 28 735 - 26 -2~ ~'? 3 4,4'-biphenylene diphosphonite and 3,9-bi~-(2,4-di-tert-butylphenoxy~2,4,8,10-tetraoxa-3,9-diphospha-spiro[5,5~undecane.

5. Peroxide-destroyina compounds t such as, for example, esters of ~-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mer-captobenzimidazole, the zinc salt of 2-mercapto-benzimidazole, zinc dibutyl-dithiocarbamate, di-octadecyl disulphide and pentaerythritol tetrakis-(~-dodecylmercapto) propionate.

6. Polyamide stabilisers, such as, for example, copper salts in combination with iodides and/or pho~phorus compounds, and salts of divalent manganese.

7. Basic costabilisers, such as, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, amines, polyamides, polyurethanes and alkali metal and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn ~tearate, Mg stearate, Na riconoleate, K palmitate, antimony pyrocatecholate or tin pyrocatecholate.

8. Nucleating ag_nt~, ~uch as, for example, 4-tert-butylbenzoic acid, adipic acid and diphenylacetic acid.

Le A 2B 735 - 27 -2 ~ ~_ r J~ .J 3 9. Fillers and reinforcinq aaents, such as, for example, calcium carbonate, silicates, glaQ~ fibres, asbestos, talc, kaolin, mica, barium sulphate, metal oxides and hydroxide~, carbon black and graphite.

10. Other additives, such as, for example, plasticiser~, lubricants, emulsifiers, pigment~, optical brighten~
ers, flameproofing agents, antistatics and blowing agents.

The ~haped articles according to the invention are obtained by mixing the individual component~. Mixinq can be carried out by known techniques in any manner, for example via kneaders or extruders. Further processing i~
carried out by the known techniques of thermopla~tic processing, for example by extrusion or injection moulding.

Shaped articles according to the pre~ent invention are neck collars, neck collar pendants (medallionQ), ear, tail and foot tapes, ear marks, films, peel-off films, adhesive strip~, strips, sheets and granules. Neck collars and medallions for dog~ and cats may be mentioned as preferred.

The shaped articles are u~ed for combating parasites on the host animal, which live on the host animal and in the environment of the host animals, such as domestic animals, pet~ and ~tock animals.

Le A 28 735 - 28 -2 ~ d ~ ~ 3 The domestic animal6, pets and ~tock animals include mammals, such as, for example, cattle, ~heep, goats, horses, pigs, dogs and cats.

The pests include:
From the order of the Anoplura, for example, Haematopinu~
8pp-, Linognathus 9pp-, Solenopotes ~pp., Pediculuq app.
and Pthiru3 spp.;
from the order of the Mallophaga, for example, Trimenopon ~pp., Menopon spp., Eomenacanthus spp., Menacanthus spp., Trichodectes spp., Felicola spp., Damalinea spp. and Bovicola 8pp.;
from the order of the Diptera, for example, Aedes spp., Culex spp., Simulium spp., Phlebotomus spp., Chrysops ~pp., Tabanus spp., Musca spp., Hydrotaea 8pp., Mu~cina 15 8pp., Haematobcsca 8pp., Haematobia 9pp., Stomoxys spp-, Fannia Bpp. ~ Gl03sina 8pp., Lucilia spp., Calliphora spp., Auchmeromyia spp., Cordylobia 9pp., Cochliomyia spp., Chry~omyia epp., Sarcophaga 9pp., Wohlfartia spp., Gasterophilus spp., Oesteromyia spp., Oedemagena spp., Hypoderma 8pp., Oestru~ 9pp., Rhinoestrus spp-, Melophagus spp. and ~ippobo6ca spp..

From tha order of the Sîphonaptera, for example, Ctenocephalides spp., Echidnophaga spp., Ceratophyllus spp..

25 From the order of the Metastigmata, for example, Hyalomma spp., Rhipicephalus ~pp., Boophilus Bpp- ~ Amblyomma app-, Haemaphy~ali~ ~pp., Dermacentor epp., Ixode~ spp., Argas Le A 28 ?35 - 29 -;~$ ~f?3 spp., Ornithodoru~ spp. and Otobius 8pp.;
from the order of the Mesostigmata, for example, Dermany8~u8 8pp., Ornithony8~UB ~pp- and Pneumony~sus 8pp ~ .

From the order of the Prostigmata, for example, Cheyletiella Bpp., Psorergates ~pp-, Myobia Bpp., Demodex ~pp. and Neotrombicula spp.;
from the order of the Astigmata, for example, Acarus spp., Myocopte~ spp., P~oropte~ ~pp., Chorioptes 8pp., Otodectes ~pp., Sarcoptes ~pp., Notoedre~ 3pp., Knemidocoptes spp., Neoknemidocoptes 8pp. Cytodites spp.
and LaminoYioptes spp..

The following example~ of in3ecticidal mouldings based on copolyether block amides are intended to illustrate the 15 invention without limiting it:

Example A

Composition:
~-Cyfluthrin 12.00 g Styrene block copolymer (Thermolast X~) 92.50 g 100.00 g Production:
The mixture is extruded to form neck collars for dog~ in a conventional msnner.

Le A 28 735 - 30 -z~
xample B

~-Cyfluthrin 10.00 g Pyriproxifen 0.35 g Triacetin 5.00 g Styrene block copolymer (Thenmolast X )~4.65 g 100 . 00 g Production:
~he active compounds and triacetin are heated together until a clear solution re~ults. Thermolast K is wetted with the warm solution of active compounds and triacetin in a mixer. The components are mixed until the mixture is homogeneous. Heating the mixture, for example as a result of increasing the speed of rotation of the mixer, pro-motes ab~orption of the solution into the styrene blockcopolymer. The mixture i~ extruded on an extruder to form sheets, from which medallions (= pendants for neck collars) of 2 x 4 cm are ctamped.

Le A 28 735 - 31 -,~

Example C

Composition:
Prcpoxur 7.50 g Styrone block copolymer (Thermolast K0) 92.50 g 100. 00 g Production:
The active aompound i8 applied to the carrier in an intensive mixer and the mixture is ~haped to form neck collars for dogs by injection moulding.

Le A 28 735 - 32 -

Claims

1. Shaped articles which contain active compounds, characterised in that they comprise, as the carrier, thermoplastic elastomers based on styrene/butylene block copolymers as well as customary additives if appropriate.

2. Processes for the production of shaped articles containing active compounds, characterised in that thermoplastic elastomers based on styrene/butylene block copolymers are mixed with active compounds and if appropriate customary additives and the mixture is processed in the customary manner.

Le A 28 735 - 33 -