AU662180B2 - 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 - Google Patents

Description

lu Our Ref: 445440 6621,80 P/00/011 Regulation 3:2

AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT C C C CC r Ct

CL

C C t C Applicant(s): Address for Service: Bayer Aktiengesellschaft D-5090 Leverkusen Bayerwerk

GERMANY

DAVIES COLLISON CAVE Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 *i 'S C C CCC rcCC C C Invention Title: 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 The following statement is a full description of this invention, including the best method of performing it known to me:- 5020 L i m d

~I

:I.

4,' r; The present invention relates to new shaped articles which contain active compounds and are based on elastomeric styrene/butylene block copolymers which can be processed as thermoplastics, 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 based on the slow release 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, Pasarela 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 0 052 411, Grubb et al US-P 3 852 416 and Pearce US-P 4 536 388).

C'

t C Ir I (rr( 20 4.4

S

4 250 The carrier employed practically almost exclusively for known shaped 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 elastomers are also possible as carrier polymers for ear marks. However, this citation also describes exclusively examples using plasticiser-containing PVC as the carrier polymer.

This is also not surprising. PVC is inexpensive and ji *4G*54 I 4 4. C 1 14 4 4 444*. C

I

Le A 28 735 1 readily accessible. It is also miscible with other substances, in particular plasticisers, within wide limits. These plasticisers in PVC bodies containing active compounds have the function of keeping the active compound dissolved in the carrier and of transporting it slowly to the surface of the body. At the surface, the active compound evaporates or is rubbed off from the surface, together with the plasticiser. The interaction of the three components PVC carrier, plasticiser and active compound determines whether and to what extent the shape% 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 reasons, it is desirable to replace PVC as the carrier material. It is also advantageous to dispense partly or completely with the use of plasticisers. 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.

Thermoplastic elastomers are materials which comprise elastomeric phases either mixed physically or bonded S chemically in polymers which can be processed as S thermoplastics. A distinction is made between polyblends, 4 6 A1 LeA 28 735 2in which the elastomeric phases are present in physically mixed-in form, and block polymers, in which the elastomeric phases are a constituent of the polymeric matrix.

Hard and soft regions are present side by side as a result of the build-up of the thermoplastic elastomers.

The hard regions form a crystalline network structure or a continuous phase, the interstices of which are filled by elastomeric segments. On the basis of this build-up, these materials have rubber-like properties.

A distinction may be made between 5 main groups of thermoplastic elastomers: 1.

2.

3.

4.

Copolyesters Polyether block amides (PEBA) Thermoplastic polyurethanes (TPU) Thermoplastic polyolefins (TPO) Styrene block copolymers t I *r 2 *t 20 t These 5 main groups show similar macroscopic physical properties, coupled with a completely different chemical build-up. In spite of these macroscopically similar properties, these main groups behave completely differently in respect of mixing in and release of active compounds.

The use of thermoplastic elastomers based on copolymers as carriers for active compounds is known. The use of styrene/butadiene block copolymers as carriers is described in EP-OS (European Published Specification) 338 821.

25 4 0 *D A a..I I 4-r 4- II 44 r~C 4.114 I+r Le A 28 735 3 0 I 1 1 1 I 1 1 11 carriers is described in EP-OS (European Published Specification) 338 732.

The present invention relates to 1. Shaped articles which contain active compounds, characterised in that they comprise, as carriers, thermoplastic elastomers based on styrene/butylene block copolymers, as well as customary additives if appropriate.

If 10 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 custova.ry additives, and the mixture is processed in the customary 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 Swithout addition of plasticisers, since this capacity is limited to only a very few polymers. If only one component of the overall system is changed, the effects are unpredictable. Thermoplastic elastomers based on thermoplastic olefins (TPO) or thermoplastic polyurethanes, for example, are not capable of allowing active compounds ".25 to migrate to the surface.

o Qi4 e *C I' Le A 28 735 4 i I i The styrene/butylene block copolymers which can be used according to the invention consist of a polyethylenebutylene rubber central block with a polystyrene end block linked chemically to both ends. The polystyrene content is less than 30%. The polystyrene end blocks are distributed uniformly in the ethylene rubber matrix as spherical polystyrene domains.

Processes 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 styrene/butylene block copolymers are obtainable, for example, under the commercial names ®Kraton G and ®Elexar from Shell Chemie GmbH and ®Thermolast-K- Compounds from Kraiburg.

Active compounds which may be mentioned for the shaped articles according to the invention are, preferably, i insecticides, in particular parasiticides, for use on animals. The insecticides include phosphorus-containing compounds, such as phosphoric or phosphonic acid esters, S 20 naturally occurring and synthetic pyrethroids, carbam- 9 cc ates, amidines, juvenile hormones and juvenoid synthetic r active compounds.

The phosphoric or phosphoric acid esters include: 0-ethyl 0-(8-quinolyl) phenyl-thiophosphate (quintiofos), 4. 4 t

I

Le A 28 735 5 I 1 0,0-diethyl 0- (3-chloro-4-methyl-7-coumarinyl) thiophosphate (coumaphos), 0. O-diethy. 0-phenyiglyoxylonitrile oxime thiophosphate (phoxim), 0 ,0-diethyl 0-cyanochlorobenzaldoxime thiophosphate (chiorphoxim), o .0-diethyl 0- (4-bromo-2 ,5-dichlorophenyl) phosphorothionate (bromophos-ethyl), 0,0,0',0'-tetraethyl-S,S'-methylene di(phosphorodithionate) (ethion), 2, 3-p-dioxanedithiol-S, S-bis (0,O-diet1Q--l phosphorodithionate, 2-Chloro-1- 4-dichiorophenyl) -vinyl diethyl phosphate 4. 1,(chlorfenvinphos), and 0,0-dimethyl 0-(3-methyl-4-methylthiophenyl) thionophosphate (fenthion).

The carbamates include: 2-isopropoxyphenyl methylcarbamate (propoxur) and 1-naphthyl N-methylcarbamate (carbaryl).

Le A 28 735-6 6 8 ii:i i~ 1; ii, i-: u The synthetic pyrethroids include compounds of the formula I

R

3 R

C

COO-CH-

RR

formula I in which

R

1 and R 2 represent halogen, optionally halogen-substituted alkyl or optionally halogen-substituted phenyl, represents hydrogen or CN, represents hydrogen or halogen and represents hydrogen or halogen, C Cr Cr C

R

5 Preferred synthetic pyrethroids are those of the formula I in which

R

I represents halogen, in particular fluorine, chlorine or bromine,

R

2 iif S* 4 4 C C I CCCr represents halogen, in particular fluorine, chlorine, bromine, trihalogenomethyl, phenyl or chlorophenyl, Le A 28 735 7 j j

R

3 represents hydrogen or CN,

R

4 represents hydrogen or fluorine and

R

5 represents hydrogen.

Particularly preferred synthetic pyrethroids are those of the formula I in which

R

1 represents chlorine, R represents chlorine, trifluoromethyl or pchlorophenyl,

R

3 represents CN,

R

4 represents hydrogen or fluorine and

(R

5 represents hydrogen.

Compounds of the formula I which may be mentioned in particular are those in which I l t R represents chlorine,

R

2 represents chlorine or p-chlorophenyl, R represents CN, Le A 28 73 8 ,1 *t 1S Le A 28 735 -8 4 41 4 L

"A

It represents fluorine in the 4-position and RD represents hydrogen.

Compounds which may be mentioned specifically are: (a-c.yano-4-fluoro-3-phenoxy)-benzyl 3-[2-(4-chlorophenyl) -2-chlorovinyl]-2,2-dimethyl-cyclopropanecarboxylate (flumethrin), a-cyano(4-fluoro-3-phenoxy) -benzyl 2,2-dimethyl-3-(2 ,2dichlorovinyl) -cyclopropanecarboxylate (cyfluthrin) and its enantiomers and stereomers, a-cyano-3,-phenoxybenzyl )-cis,trans-3-(2 ,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate (deltainethrin), a-cyano-3-phenoxybenzyl 2,2-dimethyl-3-(2,2dichlorovinyl)-cyclopropanecarboxylate (cypermethrin), 15 3-phenoxybenzyl -cis, trans- 3- 2-dichlorovinyl) -2,2 dimethylcyclopropanecarboxylate (permethrin), 4 4 ~i4 4 44 4 4 *44 4 14 4 4 44 4 *4 *4 4 4 41 4 *0 a-cyano- 3-phenoxy-benzyl (fenvalezate) and a- (p-Cl-phenyl) -isovalerate 2-cyano-3-phenoxybenzyl 2- (2-chloro-a,a~,a-trifluoro-ptoluidino)-3-methylbutyrate (fluvalinate).

*4 o :20 4

SO

*0 S 041141 4 444(44 4 4 4 4 Le A 28 735 9ma The aniidi nes include: 3-methyl-2- 4-dimethyl-phenylimino] -thiazoline, 2- (4-chloro-2-methylphenylimino) -3-methyithiazolidine, 2-(4-chloro-2-methylphenylimino) -3-(isobutyl-1-enyl) thiazolidine and (2 ,4-dimethyiphenyl) -3-methyl- 1,3, 1,4-diene (amitraz).

The juvenile hormones or substances like juvenile hormones include substituted diaryl ethers, benzoylureas and triazine derivatives. The juvenile hormones and substances like juvenile hormoi .s include, in particular, compounds of the following formulae:

H

5 C 2 C 2

H

5

CH

3

CH

3 3'o-H '0 CH 3

CH

3 C

V

Cl C C I

CC

IC 4.

44

CH

3

CH

3 CHI3 0

H

3 C N.'..CH3 a, 4 ta a. 4, a, a It C C C I LI 4~I 1' IC I C

C-

*44 EL a Le A 28 735 10

CH

3 CH 3 CH 3 0

H

3 C0

CH

3

CH

3 CH-a 0 CH 3

CH

3 N N o

H

3 C Cl kC H

H

5

C

2 0 C 2

H

5

CH

3

H

3

C

M3

)CH

3

H

3 C 0

CH

3 CH 3 0

H

3 C

OCR

3

I

I I~I 4 f ft I 4 1(4 4.

LI 4: I I

LI

I II 4 4 i 14 11 0 4 0 4.

01£ 0 0~ 0 4 644144 C I 4 14:14:4:4 C 4: 4 4:.

ilL It 4.

0 4.

The substituted diaryl ethers include, in particular, LeA 28 735 -1

A

ii; l;i substituted alkoxydiphenyl ethers or -diphenylmethanes of the general formula I

R

1 Y-(CH)n-(CH)m-X-Het R2 wherein

R

1 represents hydrogen, halogen, alkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy, halogenoalkylthio, dioxyalkylene, dioxyhalogenoalkylene, CN, NO 2 alkenyl, alkinyl, alkoxyalkyl, alkoxyalkoxy or hydroxyalkoxy,

R

2 represents the radicals mentioned for R 1 t bi I.~ *1r

R

3 represents the radicals mentioned for R 1

R

4 represents hydrogen, halogen, alkyl, halogenoalkyl or

R

5 represents the radicals mentioned for R 4 Het represents optionally substituted heteroaryl, which is not bonded to the rest of the radical via the hetero atom, s( C C C V (r i

C

Le A 28 735 12 cB r ii i:

R

r i

I-

t t I a a at

F

C

I Cr

I:

ttaA~

C,

X and Y independently of one another represent or -S- Z represents -CH 2

-CHCH

3 or -C(CH 2 2 and m and n independently of one another represent 0, 1, 2 .or 3, but their sum is equal to or greater than 2.

Particularly preferred compounds of the formula I are those in which

R

1 represents hydrogen, methyl, trifluoromethyl, methoxy, trifluoromethoxy, chlorine or fluorine

R

2 represents hydrogen,

R

3 represents hydrogen, fluorine, chlorine or methyl,

R

4 represents hydrogen or methyl,

R

5 represents methyl, ethyl, trifluoromethyl or hydrogen, Het represents pyridyl or pyridazinyl, which are optionally substituted by fluorine, chlorine, methyl, NO 2 methoxy or methylmercapto, X represents 0, Le A 28 735 13 y z m n The represents 0, represents 0, CH 2 or -C(CH 3 2 represents 1 and represents 1.

following compounds may be mentioned specifically: 44 ~t4 I 4 4 8 .4 4 0 4 4 1 -i 6

R

3

H

H

H

H

H

H

H

CH

3

CH

3

CH

3

CF

3 C 2

H

5

H

CH

3

CH

3

H

2-Cl

H

H

H

H

H

H

0 0 0 0 0 0

CH

2 C CH 3 2 t4 t C C C C Ci it C C C £4444 4 £t4~4 4 4444 C 4 44,4 4 4.4444 4 4 Le A 28 735 14 K~z\ E~ O-H 2

-CHQ--R

R

1

R

3 H H CH 3 z -O(CH 2 3 O0Het 44: 4:4: 4:4:4 '4: 4 4: 4 4:11 4: 4:1. 1 1 4:4: 4 4:4 4: 44: I 4 4:.

4: *4: 1.4: 4 4: 44 4: 44 R 1 R 3 z He t

N-

H H H H H H

N

N-N

4 Gas 0 04 4 044-) Le A 28 735 15 Le A-28 735 -2

L

The benzoylureas include compounds of the formula C wherein R2 R 3

R

4 44 4 444 44 4 10 444 4 44 4 4 4 44 4 *4* 4 4 4 94 14 4 4 44 44 represents halogen, represents hydrogen or halogen, represents hydrogen, halogen or C 1 -4-alkyl and represents halogen, 1-5-halogeno-C..

4 -alkyl, C1alkoxy, 1-5-halogeno-Cl.

4 -alkoxy, C 1 4 -alkylthio, halogeno-C 1 4 -alkylthio, phenoxy or pyridyloxy, which can optionally be substituted by halogen, C 1 alkyl, 1-5-halogeno-C 1 l.

4 -alkyl, C 1

I

4 -alkoxy, C,-4-alkoxy, C 1 4 -alkylthio or 1-5-halogeno-Cl-C 4 alkylthio.

~t 4 4 4 4 44~ 44454

S

414 4~ 4444 4 4 441494 4 4 The following compounds may be mentioned in particular:

NHCONHQ::>R

4 LeA28 735 -16-

I'

CF

3

CF

3

CF

3

CF

3

SCF

3

SCF

3

SCF

3

OCF

3

OCF

3

OCF

3 0-K

F

3

-CF

3 It It t $If I 14 4 1 I 444 t I 14 4 44 4~ 14 Is 4 4 1

II

44 The triazines include compounds of the formula (VI)

NH-R

1

R

2 -HN

NH-R

3

(VI)

ft 4 Is Is (Is IT 4 t

I

I

i 4 #44414 4 4 *4 0 gl 4.

U

4040 44)004 Le A 28 735 17

A

~1 wherein R, represents cyclopropyl or isopropyl; 10 4 r4 r 4 t

R

2 denotes hydrogen, halogen, Cl-Cl 2 -alkylcarbonyl, cyc lopropylcarbonyl, Cl-C 2 -alklcarbamoyl, C 1

-C

12 alkyithiocarbamoyl or C 2 -C-alkenylcarbanioyl; and

R

3 represents hydrogen, C 1

-C

12 -alkyl, CYClopropyl, C 2

-C

6 alkenyl, Cl-C 2 -alkylcarbonyl, cyclopropylcarbonyl, Cl-C 2 -alkylcarbamoyl, C 1

-C

12 -alkylthiocarbanoyl or

C

2 -C-alkenylcarbaxnoyl, and acid addition salts thereof which are non-toxic to warm-blooded animals.

Compounds which may be mentioned in particular are:

R

1 R 2 R 3 Cyc lopropyl Cyc lopropyl Cycl1opropyl Cyc lopropyl

H

CH

3

C

2

H

C

3

H

7 -n 45s**4 4 4 a is.., 4 4.4.

a 5145 *444 8e a Le A 28 735 1j.~ 21 ~i4 Example C (Continuation)

E~

r d~4t t ~t 1V~ t'x t t L t t *14*~G *s S 54 5 5,45 q 54 5~45*5 S

S

Cyc lop ropyl Cyc lopropyl Cyclopropyl Cycl1opropyl Cyclopropyl Cyc lopropyl Cyclopropyl Cyc lopropyl Cycl1opropyl Cyc lopropyl Cyc lopropyl Cyc lopropy1 Cyc lopropyl Cye lopropyl Cycl1opropyl Cyclopropyl Cycl1opropyl Cyc lopropyl Cyc lopropyl Cyclopropy-l Cycl1opropyl Cyc lopropyl Cyclopropyl Cyc lopropyl Cyc lopropyl Cyc lopropyl Cyc lopropyl Le A 28 735

H

H

H

H

H

H

H

H

H

Cl c I Cl Cl

H

H

H

H

H

H

H

H

H

H

H

COCH

3

COC

3

H

7 -n

COCH

3

C

4

H

9 -n

CSH

1 1 -n

C

6

H

1 3 -n

C

7

H

1 5 -r

C

8

H

1 7 -ri

C

1 2

H

2 5 -ri

CH

2

-C

4

H

9 -t

CH

2

CH(CH

3

)C

2

H

CH

2

CH=CH

2 C 2

H

C

6 Hl 3 -n

C

8

H

1 7 -n

C

1 2

H

2 5 -n Cyc lopropyl

COCH

3 COCH3.HC1

COC

2

H

5 *HC1

COC

2

H

5

COC

3

H

7 -n

,COC

3

H

7 -i

COC

4

H

9 -t*HC1

CCC

4 H9-n

COC

6

H

1 3 -n C0C 1 1

-H

2 3 -n

COC

2

H

C0C 6 Hl 3 -ri Coc 3

H

7 -n

I

I

I

~i I 19 (Continuation) Cyclopropyl 3O~H CO 3 7 Cyclopropyl H COCyclopropyl Cyclopropyl COCylclopropyl COCyclopropyl Cyclopropyl COCH 3

CH

3 Isopropyl H H Isoprpyl HCOCH 3 Isopropyl H CO 3 U CclproylH CONC -n Iysopropyl H OH 3

H

7 Cyclopropyl CHC CONHCH 3 Cyclopropyl H CSWHC 3 7I Cyclopropyl H CSNHCH3C=H Cyclopropyl CHCCCH CONHCH 2

CH=CH

2 Cyclopropyl CSNHCH 3

CSNHCH

3 4.The active compounds having the comnon names propoxur, cyfluthrin, flumethrin, pyriproxyf en, methoprene, Diazinon, amitraz and fenthion may be singled out in particular.

The active compounds can be present in the shaped articles by themselves or as a mixture with one another.

The active compounds are present in the shaped articles in concentrations of 0.1 -20 by weight, preferably of JO between 1 and*10 by weight.

*The shaped articles according to the invention can furthermore comprise the additives customary f or plastics. Customary additives are, f or example, pigments, LeA-28 735 I momd stabilisers, f low agents, lubricants and mould release agents.

Examples of customary additives are: 1. Antioxidants 1.1 Alkylated mono~henols, for example 2,6-di-tertbutyl-4-methylphenol, 2-tert-butyl-4, 6-dimethylphenol, 2, 6-di-tert-butyl-4-ethylphenol, 2, 6-ditert-butyl-4-n-butylphenol, 2, 6-di-tert-butyl-4-ibutylphenol, 2, 6-di-cyclopentyl-4-methylphenol, 2- 10 (a-methyl-cyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol and 2,4, 6-tricyclohexylphenol, 2, 6-di-tert-butyl-4-methoxymethylphenol.

1.2 Alkylated hydroquinones, for example 2,6-di-tertbutyl-4-methoxyphenol, 2, 2,5-di-tert-aniyl-hydroquinone and 2,6diphenyl-4-octadecyloxyphenyl.

1.3 Hvdroxvlated thiodiphenyl ethers, for example 2,2'thio-bis- (6-tert-butyl-4-methylphenol), 2,2 '-thio- 14 bis-(4-octylphenol), 4,4 '-thio-bis-( 6-tert-butyl-3methylphenol) and 4,4 '-thio-bis-( 6-tert-buty-.2methylphenol).

*1.4 Alkvylidene-bis~henols, for example 2,2'-methylenebis- (6-tert-butyl-4-methylphenol), 2,2 '-methylenebis-(6-tert-butyl-4-ethylphenol), Le A28 735 -21- Le A 28 735-- 8

I

F

a S rat 4. .a a 4 a ass 4~ ft a a a a .d a a.

at 4.

ca.a~: i to.

2,2' -methylene-bis- (4-methyl-6 (c-methylcyclohexyl) phenol, 2,2' -methylene-bis- (4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis-(6-nonyl-4-methylphenol), 2,2' -methylene-bis- 6-di-tert-butylphenol), 2,2 '-ethylidene-bis-(4 ,6-di-ter-t,hutylphenol), 2,2'-ethylidene-bis-(6-tert-butyl4isobutyiphenol), 2,2'1-methylene-bis-[6-(a-methylbenzyvl) -4-nonylphenolJ, 2,2 '-methylene-bis-[6-(a,cdimethylbenzyl) -4-nonylphenol], 4,4 '-methylene-bis- (2,6-di-tert-butylphenol), 4,4 '-methylene-bis- (6tert-butyl-2-methyiphenol), 1, 1-bis- 4-hydroxy-2-methylphenyl) -butane, 2, 6-di- (3-tertbutyl-5-methyl-2-hydroxybt rzyl) -4-methylphenol, 1,1, -Iris- (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1, 1-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl -3-n-dodecylmercaptobutane, ethylene glycol bis- 3-bis- (3 '-tert-bt'tyl-4 '-hydroxyphenyl) butyrate], di-(3-tert-butyl-4-hydroxy-5-methylpheny.) -dicyclopentadiene and di- (3 '-tert-butyl- 2' -hydroxy-5' -methylbenzyl )-6-tert-butyl-4-methylphrwyl] terephthalate.

BezvYl. compounds, for example 1,3,5-tri-(3,5-ditert-butyl-4-hydroxybenzyl) 6-trimethylbenzenie, di- 5-di-tert-butyl-4-hydroxybenzyl) sulpLitde, isaoctyl 3, 5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetate, bis- (4-tert-butyl-3-hydroxy-2 ,6-dimethylbenzyl) dithiol-terephthalate, 1,3, 5-tris- tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5tris- (4-tert-butyl-3-hydroxy-2 ,6-dimethylbenzyl) Le A 28 735 -2 22

WV

isocyanurate, dioct4decvl 3, 5-di-tert-butyl-4hydroxybenzyl-phosphonate and 3, 5-di-tert-butyl-4hydroxybenzyl-phosphonic acid monoethyl ester calcium salt.

1.6 Acylaminophenols, for example 4-hydroxy-lauric acid anilide, 4-hydroxystearic acid anilide, 2,4-bisoctylmercapto-6- 5-di-ter-t-butyl--4-hydroxyanilino) -s-triazine and octyl Ni-(3, 5-di-tert-butyl-4hydroxyphenyl) -carbamate.

I0 1.7 Esters of B-(3,5-di-tert-butyl-4-hydroxyphenyll- Propionic acid with mono- or polyhydric alcohols, such as, for example, methanol, octadecanol, 1,6hexanediol, neopentyl glycol, thiodiJethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-hydroxyethyl isocyanurate and di-hydroxyethyl-oxalic acid diamide.

1.8 Esters of 6- (5-tert-butvl-4-hvdroxv-3-methylnhenyl) Propionic acid with mono- or polyhydric alcohols, such as, 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 A- (3,5-di-tert-butv1-4-hvdroxY~henyll Pronionic acid, s~uch as, for example, di-tert-butl-4-hydroxyphenylpropionyl)- I I

'C

II

I4* t4 .c *4*e

I

U

Le A 28 735 23 MEL., I I I l1 hexamethylenediamine, N,N' 5-di-tert-butyl-4hydroxyphenyipropionyl) -trimethylenediamine and N ,N'I (3 ,5-di-tert-butyl-4-hydroxyphenylpropionyl)- hydrazine.

2. UV absorbers and light stabilisers 2.1 2-(2'-Hvdroxvphenyl)-benzotriazoles, such as, for example, the 5'-methyl, 3',5'-di-tert-butyl, tert-butyl, 1, 3, 3-tetramethylbutyl) 315 '-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' benzyl) derivative.

2.2 2-Hydroxvbenzophenones, such as, for example, the 4hydroxy, 4-metLhoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydoxy and 2'-hydroxy- 4,4"-dimethoxy derivative.

4L 2.3 Esters of optionally substituted benzoic acids, such as, for example, 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis-(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 2, 4-di-tert-butylphenyl 3, tert-btityl-4-hydroxybenzoate and hexadecyl tert-butyl-4-hydroxybenzoate.

2.4 Acrylates, such as, for example, ethyl or isooctyl a-cyano-fl, f-diphenylacrylate, methyl a-carbomethoxy- 2 Le A 28 735 24 cinnamate, methyl or butyl a-cyano-p-methyl-pmethoxy-cirinamate, methyl a-carbomethoxy-p-methoxycinnamate and N- (p-carbomethoxy-e-cyanovinyl) -2methyl-indoline.

2.5 Nickel compounds, such as, for example, nickel complexes of 2,2'-thio-bis-[4-(1,l,3,3-tetramethylbutyl)-phenol], such as the 1:1 or 1:2 complex, optionally with additional ligands, such as nbutylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyl-dithiocarbamate, nickel salts of 4-hydroxy-3 phosphonic acid monoalkyl esters, such as of the methyl or ethyl ester, nickel complexes of ketoximes, such as 2-hydroxy-4-methyl-phenyl undecyl ketone oxime, and nickel complexes of 1-phenyl-4optionally with additional ligands.

2.6 Sterically hindered amines, such as, for example, bi-2266ttrmty.prdl)sbctbs 20bi(12,2,6,6-etamethylpiperidyl) sebacate, bis- 6-pentamethylpiperidyl) n-butyl-3, t tert-butyl-4-hydroxybenzyl-malonate, the condensation product of 1-hydroxyethyl-2 6-tetramethyl- 4 -hydroxypiperi dine and succinic acid, the condensation product of N,N'-(2,2,6,6-tetramethyl-4piperidyl)-hexamethylenediamine and 4-tertoctylamino-2 ,6-dichloro-1, 3, 5-s-triazine, tris- 4. 6-tetramethyl-4-piperidyl) nitrotriacetate, 4 1 Le A 28 735 tetrakis- 6-tetramethyl-4-piperidyl) -1,2,3,4butanetetracarboxylic acid and 1,1 ethanediyl) -bis- 2.7 Oxalic acid diamides, such as, f or example, 4,4'-dioctyloxy-oxanilide, 2,2 '-di-octyloxy-5 -di-tertbutyl-oxanilide, 2,2' -di-dodecyloxy-5 -di-tertbutyl-oxanilide, 2-ethoxy-2 '-ethyl-oxanilide, N,N'bis- (3-dimethyl-aminopropyl) -oxalamide, tert-butyl-2'I-ethyloxanilide and its mixture with 2ethoxy-2' -ethyl-5, 4'-di-tert-butyl-oxaniliLde and mixtures of o- and p-methoxy- and of o- and pethoxy-disubstituted oxanilides.

3. Metal deactivators, such as, for example, N,N'- CC diphenyloxalic acid diamide, N-salicylal-N I -salicyl- C ;15 oylhydrazine, N,N'-bis-(salicyloylhydrazine, N,N'benylieneoxaicacid dinadrazide.

4. Phosrhites and Rhosphonites, such as, for example, triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tri-(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris- 4-di- CC~tI ~tert-butylphenyl) -phosphite-, diisodecylpentaerythritol diphosphite, di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, tristearyl-sorbitol 4 ~..triphosphite, tetrakis- 4-di-tert-butylphenyl)- Le A-28735 -26- 4,4' -biphenylene diphosphonite and 3, 9-bis- 4-ditert-butylphenoxy-2, 4,8, 10-tetraoxa-3, 9-diphospha- Peroxide-destroingr comounds, such as, f or example, esters of pl-thiodipropionic acid, for example the lauryl, zstearyl, myristyl or tridecyl ester, mercaptobenzimidazole, t.Sie zinc salt of 2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyl disulphide and pentaerythritol tetrakis- (p-dodecylmercapto) -propionate.

6. Polvamide i-tabilisers, such as, for example, copper salts in comnbination with iodides and/or phosphorus t 11 compounds, and salts of divalent manganese.

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

8. Nucleatincr acients, such as, for example, 4-tertbutylbenzoic acid, adipic acid and diphenylacetic acid.

Le A28 735 -27- -28- 9. Fillers and reinforcing agents, such as, for example, calcium carbonate, silicates, glass fibres, asbestos, talc, kaolin, mica, barium sulphate, metal oxides and hydroxides, carbon black and graphite.

Other additives, such as, for example, plasticisers, lubricants, emulsifiers, pigments, optical brighteners, flameproofing agents, antistatics and blowing agents.

The shaped articles according to the invention are obtained by mixing the individual components. Mixing can be carried out by known techniques in any manner, for example via kneaders or extruders. Further processing is carried out by the known techniques of thermoplastic processing, for example by extrusion or injection moulding.

Shaped articles according to the present invention are articles indicated, in this specification, as articles "as herein defined". Shaped articles, as herein defined, are i articles selected from the group comprising neck collars, neck collar pendants (medallions), ear, tail and foot tapes, ear marks, films, peel-off films, adhesive strips, S: i 20 strips, sheets and granules. Neck collars and medallions for dogs and cats may be i mentioned as preferred.

The shaped articles are used 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, 25 pets and stock animals.

t t t c c* 4 p:\wpdocs\grs\445440\jgs The domestic animals, pets and stock animals include mammals, cvich as, for example, cattle, sheep, goats, horses, pigs, dogs and cats.

The pests include: From the order of the Anoplura, for example, Haematopinus spp., Linognathus spp., Solenopotes spp., Pediculus spp.

and Pthirus spp.; from the order of the Mallophaga, for example, Trimenopon spp., Menopon spp., Eomenacanthus spp., Menacanthus spp., Trichodectes spp., Felicola spp., Damalinea spp. and Bo-.-Iola spp.; from the order of the Diptera, for example, Aedes spp.

Culex spp., Simulium spp., Phlebotomus spp., Chrysops spp, Hemaobocaspp., Haematobia spp., Stomoxys spp., Fannia spp., Glossina spp.,~ Lucilia spp., Calliphora spp., Auchmeromyia spp., Cordylobia spp., Cochliomyia spp., Chrysomyia spp., Sarcophaga spp., Wohlfartia spp., Gasterophilus spp., Oesteromyia spp., Qedemagena spp., Hypoderma spp., Oestrus spp., Rhinoestrus spp., Melophagus Bpp. and Hippobosca spp..

From the order of the Siphonaptera, for example, Ctenocephflidies s00.. Echidnophaaa spp.. Ceratophvllusj a.P.

25 From the order of the Metastigmata for example, Hyalomma 4 spp., Rhipicephalus spp., Boophilus spp., Aniblyoinma spp., 'aHaemaphysalis spp., Dermacentor spp., Ixodes spp., Argas Le A28 735 -29- I I spp., Ornithodorus spp. and Otobius spp.; from the order of the Mesostigmata, for example, Dermanyssus spp., Ornithonyssus spp. and Pneumonyssus spp..

From the order of the Prostigmata, for example, Cheyletiella spp., Psorergates spp., Myobia spp., Demodex spp. and Neotrombicula spp.; from the order of the Astigmata, for example, Acarus spp., Myocoptes spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Neoknemidocoptes spp. Cytodites spp.

and Laminosioptes spp..

The following examples of insecticidal mouldings based on copolyether block amides are intended to illustrate the i" t15 invention without limiting it: t ~Example A Composition: p-Cyfluthrin 12.00 g Styrene block copolymer (Thermolast KO) 92.50 g 100.00 g Production: The mixture is extruded to form neck collars for dogs in a conventional manner.

Le A 28 735 i Example B p-Cyfluthrin 10.00 g Pyriproxifen 0.35 g Triacetin 5.00 g Styrene block copolymer (Thermolast K*)84.65 g 100.00 g Production: The active compounds and triacetin are heated together until a clear solution results. ThermIlis' K is wetted with the warm solution of active compo, and triacetin in a mixer. The components are mi:,-id until the mixture is homogeneous. Heating the mixture, for example as a result of increasing the speed of rotation of the mixer, pro- 15 motes absorption of the solution ii-to the styrene block copolymer. The mixture is extruded on an extruder to form sheets, from which medallions pendants for neck tic t collars) of 2 x 4 cm are stamped.

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~u s i11 Le A 28 735 31 I t Exapl C; Composition: Propoxur Styrene block copolymer (Thermolast K®) 7.50 g 92.50 g 100.00 g Production: The active compound is applied to the carrier in an intensive mixer and the mixture is shaped to form neck collars for dogs by injection moulding.

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Claims (6)

1. Shaped articles, as herein defined, for animals, wherein the said articles (i) contain one or more parasiticidal active compounds to be released therefrom for combating parasites which live on, or in the environment of, said animals, and (ii) are characterised in that they are comprised of thermoplastic elastomers based on styrene/butylene block copolymers.

2. Shaped articles according to claim 1 in which the active compounds are comprised of phosphorus-containing compounds, naturally occurring and synthetic pyrethroids, carbamates, amidines, juvenile hormones and juvenoid synthetic active compounds.

3. Shaped articles according to claim 1 or 2 in which the active compounds are phosphoric or phosphoric acid esters selected from: O-ethyl O-(8-quinolyl) phenyl-thiophosphate (quintiofos), Ct O,0-diethyl O-(3-chloro-4-methyl-7-coumarinyl) thiophosphate (coumaphos) CC' C O, O-diethyl O-phenylglyoxylonitrile oxime thiophosphate (phoxim) 4 O,0-diethyl O-cyanochlorobenzaldoxime thiophosphate (chlorphoxim) O,O-diethyl O-(4-bromo-2,5-dichlorophenyl) phosphorothionate (bromophos-ethyl) O,O,O',O'-tetraethyl-S,S'-methylene di(phosphorodithionate) (ethion) 2, 3-p-dioxanedithiol-S, S-bis(O,O-diethyl) phosphorodithionate 2-Chloro-1-(2,4-dichlorophenyl)-vinyl diethyl phosphate (chlorfenvinphos) Nr 2) 34 0, 0-dimethyl O-(3-methyl-4-methylthiophenyl) thionophosphate (fenthion).

4. Shaped articles according to claim 1 or 2 in which the active compounds are carbamates selected from: 2-isopropoxyphenyl methylcarbamate (propoxur) 1-naphthyl N-methylcarbamate (carbaryl). Shaped articles according to claim 1 or 2 in which the active compounds are synthetic pyrethroids are of the formula 1 R 3 R I CO-H_ formula I R 2COOP 4 PR C (t L C fC; C CC C C C E t 4 I in whk 20 R' and 25 R4~

6. R 2 W 2 represent halogen, optionally halogen-substituted alkyl or optionally halogen- substituted phenyl, represents hydrogen or CN, represents hydrogen or halogen and represents hydrogen or halogen, Shaped articles according to claim 5 in which represents halogen, represents halogen, trihalogenomethyl, phenyl or chlorophenyl, p: \wpdo=\grs\445440\jgs .1 I I I E.g ~4- 35 I 4-Ct (C C 4- II 4- 4- (4- I 4- 1.1.4- 1. 4-4-1.4- C 1 4- CC C C C 1 4- C I :4-4-C Cc I C 4- CC C 4--

44-4-C C 4 C R 3 represents hydrogen or CN, i represents hydrogen or fluorine and RI represents hydrogen. 7. Shaped articles according to claim 6 in which R' represents chlorine, RI represents chlorine or p-chlorophenyl, R 3 represents CN, R 4 represents fluorine in the 4-position and RI represents hydrogen. 8. Shaped articles according to claim 1 or 2 in which the active corn ounds are selected from: (a-cyaxio-4-fluoro-3-phenoxy)-benzyl 3-[2-(4-chlorophenyl)-2-chlorovinyl]-2,2-dimethyl- cyclopropanecarboxylate (flumethrin), a-cyano(4-fluoro-3-phenoxy)-benzyI 2, 2-dimethyl-3-(-2 ,-2-dichlorovinyl)-cyclo- propanecarboxylate (cyfluthrin) and its enantiomers and stereomers, d no-3-phenoxybenzyl ,trans-3-(2 ,2-dibromovinyl)-2 ,2-dimethylcyclo- 30 propanecarboxylate (deltamethrin) a-cyano-3-phenoxybenzyl 2 ,2-dimethyl-3-(2,2-e,,chlorovinyl)-cyclopropanecarboxylate ~\(cypermethrin), ~L)P:\wpdocs\grs \445440\jgs I mm I -36- 3-phenoxybenzyl trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (permethrcn), a-cyano-3-phenoxy-benzyl a-(p-C1-phenyl)-isova-ier-ate (fenvalerate) and 2-cyano-3-phenoxybenzyl 2-(2-chloro-a, a, a-trifluoro-p-toluidi~no)-3-methylbutyrate (fluvalinate). 9. Shaped articles according to claim 1 or 2 in which the active compounds are amidines selected from: 3-methyl-2-[2,4-dimethyl-phenylimino]-thiazoline, 2-(4-chloro-2-methylphenylimino)-3-methylthiazolidine, z-(4t-cIloro-2-mehylphenyuimino)--(souyl- i-eniyl)-tiiazohuinean 15,-bis-(2 ,4-dlimethylphenyl)-3-methyl- 1,3 ,5-triazaprcu ca-i1,4-diene (amitraz). Shaped articles according to claim 1 or 2 in which the active compounds are juvenile hormones or substances like juvenile hormones selected from substituted diaryl ethers, benzoylureas and triazine derivatives. 25 11. Shaped articles according to claim I or 2 in which the active compounds are substituted alkoxydiphenyl ethers or -diphenylmethanes of the general formula Ri Y-(CH)n-(CH)m-X-Het R 3 wherein VU p:\wpdocs\grs\444\jgsi -37 R 1 represents hydrogen, halogen, alkyl, alkoxy, alkylthio, halogenoalkyl, halogenoalkoxy, hal genoalkylthio, dioxyalkylene, dioxyhalogenoalkylene, CN, NO 2 alkenyl, alkinyl, alkoxyalkyl, alkoxyalkoxy or hydroxyalkoxy, R 2 represents the radicals mentioned for R', R 3 represents the radicals mentioned for R 1 R 4 represents hydrogen, alkyl, halogenoalkyl or halogen, R 5 represents the radicals mentioned for R 4 Het represents optionally substituted heteroaryl, which is not bonded to the rest of the radical via the hetero atom, X represents O, L Y represents O, Z represents O, CH 2 or -C(CH 3 2 m represents 1 and M 4 I n represents 1. 6 4 4 44 I, *12. Shaped articles according to claim 1 or 2 in which the active compounds are compounds of the formula C k: 1 CH2-CH-u p:\wpdocs\grs\445440\jgs I 46-9 38 Gil 3 Gil 3 CH 3 CF 3 CAH H Gil 3 CH,, H 2-Cl H H H H H H 0 0 0 0 0 0 Gil 2 C(CH 3 2 13. Shaped articles according to claim 1 or 2 in which the active compounds are benzoylureas of ble fori 11 C t~* C C C C C r. 20 R3 -NH-C ONH-<KL-4 wherein R' represents halogen, R 2 represents hydrogen or halogen, R 3 represents hydrogen, halogen or C 14 -alkyl and 9* I S 000 S eels 90 e9 9 0 4C I C C CC -C C CL CCL. C C C C RI represents halogen, 1-5-halogeno-C 1 -4-alkyl, C, 1 4-alkoxy, l-5-halogeno-CI- 4 -alkoxy, C 1 4-alkylthio, 1-5-halogenio-C 1 -4-alkylthio, phenoxy or pyridyloxy, which can optionally be substituted by halogen, C 14 -alkyl, 1-5-halogeno-C 1 -4-alkyl, C14- alkoxy, 1-5-halogeno-C 1 4 -alkoxy, CI-4-alkylthio or 1 -5-halogeno-Cl-C 4 -alkylthio. p: \wpdocs\grs\445440\jgs 0 -39- 14. Shaped articles according to claim 1 or 2 in which the active compounds are triazines of the formula H-Ri1 R 2 -HN NH-R3 wherein R, represents cyclopropyl or isopropyl; R, denotes hydrogen, halogen, Cl-C2-alkylcarbonyl, cyclopropylcarbonyl, C 1 -C2- alkylcarbamoyl, Cl-C-alkylthiocarbamoyl or C 2 -C 6 -alkenylcarbamoyl; and R represents hydrogen, C-C,-alkyl, cyclopropyl, C 2 -C 6 -alkenyl, Ci-Cu- alkylcarbonyl, cyclopropylcarbonyl, C,-C 1 -alkylcarbamoyl, C,-C12- I alkyithiocarbamoyl or C 2 -C 6 -alkenylcarbamoyl, CI. I 15. Shaped articles according to claim 1 or 2 in which the active compounds are selected from propoxur, cyfluthrin, flumethrin, pyriproxyfen, methoprene, Diazinon, amitraz and fenthion. S16. Shaped articles according to any one of the preceding claims which further :25 comprise customary plastics additives. 17. Process for the production of shaped articles according o claim 1 characterised in that said thermoplastic elastomers based on styrene/butylene block copolymers are mixed with said one or more parasiticidal active compounds. s 0 J a$5~ j)Awpdocrs\44544\jgs 40 18. Process for the production of shaped articles according to claim 16 characterised in that said thermoplastic elastomers based on styrene/butylene block copolymers are mixed with said one or more parasiticidal active compounds and said customary plastics additives. DATED this 16th day of June, 1995. BAYER, AKTJ]ENGESELLSCHAYI By Its Patent Attorneys, DAVIES COLLISON CAVE ~tS f t t~ 4 4- 1, VL I r I 4-4- 4- 44 4' 4 454 S 4 44 44 4 4 4 41 I 1.14-4- II 44-4-4- I C p:\wp~docs\grs\445440\jgs :I a ;_i3 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 Abstract Ct CCt 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. c (E C A; 4 4 Le A 28 735 I i;