New 3-arvibenzofuranones with electron-withdrawing substituents as stabilizers The present invention relates to novel 3-arylbenzofuranones, to compositions comprising an organic material, preferably a polymer or a lubricant, and to the novel stabilizers, as well as to the use thereof for stabilizing organic materials against oxidative, thermal or light-induced degradation and to the use of the novel stabilizers as scavengers for the oxidized developer (also termed hereafter Dox scavengers) in color photographic material.

It is well known that one of the problems associated with color photography is the diffusion of the oxidized color developer away from the light sensitive silver halide emulsion layer in which it is formed into another silver halide emulsion layer, which can result in the formation of unwanted dyes at undesired places. For instance, while being generated in the green sensitive layer and forming a magenta dye through a coupling reaction with the incorporated magenta coupler, the oxidized developer can also diffuse to the red sensitive layer thereby producing unwanted cyan dye or to the blue sensitive layer thereby producing unwanted yellow dye. This kind of color formation in the wrong layers will damage the color balance of the photographic image and thus results in poor color reproduction. One way of circumven- ting this problem is to incorporate oxidized developer scavengers in interlayers between the light sensitive silver halide emulsion layers. These scavengers should have additional pro- perties such as low tendency to migrate, good stability towards aerial oxidation and high solubility in photographic oils.

Hydroquinone derivatives which are useful as scavengers for oxidized developers are for example described in U. S. Patent 4, 345, 016.

The use of some 3-phenyl-3H-benzofuran-2-ones as stabilizers for organic polymers is dis- closed, inter alia in WO-A-80/01566 and U. S. Patent 5, 516, 920.

It has now been found that a selected group of 3-arylbenzofuran-2-ones with electron-with- drawing substituents is particularly suitable for use as stabilizers for organic materials that are susceptible to oxidative, thermal or light-induced degradation. These new compounds are also particularly suitable as Dox scavengers in color photographic material.

Accordingly, the invention relates to compounds of the formula I wherein, when n is 1, R, is a radical of the formula II, III or IV and when n is 2, R2, R3, R4 and R5 are each independently of one another hydrogen, chloro, hydroxyl, C,-C25- alkyl, C7-C9phenylakyl, unsubstituted or C1-C4alkyl-substituted phenyl ; unsubstituted or C,-C4alkyl-substituted CS-Cecycloalkyl ; C1-C18alkoxy, C1-C18alkylthio, C1-C4alkylamino, di- (C1-C4alkyl) amino, C,-C25alkanoyloxy, C,-C25alkanoylamino, C3-C25alkenoyloxy, C3-C25alka- noyloxy which is interrupted by oxygen, sulfur or # N-R18; C6-Cgcycloalkylcarbonyloxy, benzoyloxy or C,-C, 2alkyl-substituted benzoyloxy ; or each pair of substituents R2 and R3 or R3 and R4 or R4 and R5 together with the linking carbon atoms, forms a benzene ring ; or R4 is additionally- (CH2) p-COR, g or- (CH2) qOH, or when R3, R5 and R6 are hydrogen, R4 is additio- nally a radical of the formula V (V) V) wherein R, is as defined above for n = 1, R6 is hydrogen or a radical of the formula VI (VI) in which R4 is not a radical of the formula V and R, is as defined above for n = 1, R7, R8, R9, R10, R11, R12, R13, R14 and R, 5 are each independently of one another hydrogen, fluoro, fluoro-substituted C1-C12alkyl; -CN, -SOR26,-S02R26 or SOsRze ; with the proviso that at least one of R7, R8, Rg, R, o, R", R, 2, R, 3, R, 4 or Ris is not hydrogen, R16 and R17 are each independently of one another phenylen or naphthylene which are substituted by fluoro, fluoro-substituted C,-C, 2alkyl,-CN, R, 8 is hydrogen or C1-C8alkyl, R20 and R2, are each independently of one another hydrogen, CF3, C,-C, 2alkyl or phenyl, or R20 and R21 together with the linking carbon atom, form a Cs-Cacydoatkytidene ring which is unsubstituted or substituted by 1 to 3 C,-C4alkyl groups ; R22 is hydrogen, hydroxyl, C1-C25alkyl, C7-C9phenylalkyl, unsubstituted or C,-C4alkyl-substituted phenyl ; unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkyl ; or C3-C25alkyl which is interrupted by oxygen, sulfur or N-Reg R23 is C1-C25alkyl, C7-C9phenylalkyl, unsubstituted or C,-C4alkyl-substituted phenyl ; unsub- stituted or C,-C4alkyl-substituted C5-C8cycloalkyl ; or C3-C25alkyl which is interrupted by oxy- gen, sutfurorN-Rg, R24 and R25 are each independently of one another hydrogen, C1-C25alkyl, hydroxyl-substi- tuted C2-C24alkyl ; C3-C25alkyl which is interrupted by oxygen, sulfur or N-R, e ; C7-Cg- phenylalkyl which is unsubstituted or is substituted on the phenyl ring by C,-C4alkyl ; or C3-C24alkenyl ; or R24 and R25, together with the nitrogen atom to which they are attached, form a 5-, 6-or 7-membered heterocyclic ring which is unsubstituted or is substituted by C,-C4alkyl or is interrupted by oxygen, sulfur or N-Reg R26 is hydrogen or C,-C2salkyl, R27 and R28 are each independently of one another hydrogen, C1-C25alkyl, hydroxyl-substi- \ tuted C2-C24alkyl ; C3-C25alkyl which is interrupted by oxygen, sulfur or N-R, 8 ; C7-C9- phenylalkyl which is unsubstituted or is substituted on the phenyl ring by C,-C4alkyl ; or C3-C24alkenyl ; or R27 and R28, together with the nitrogen atom to which they are attached, form a 5-, 6-or 7-membered heterocyclic ring which is unsubstituted or is substituted by C,-C4alkyl or is interrupted by oxygen, sulfur or # N-R18, R29 and R30 are each independently of one another hydrogen, C1-C18alkyl or C7-C9phenyl- alkyl, or R29 and R30 together with the nitrogen atom to which they are attached form a 5-, 6- or 7-membered heterocyclic ring which is unsubstituted or is substituted by C,-C4alkyl or is interrupted by oxygen, sulfur or N-Rg, Xi is a direct bond, C1-C18alkylene, C2-C18alkylene which is interrupted by oxygen, sulfur or N-R, 8 ; C2-C, ealkenylene, C2-C2oalkylidene, C7-C20phenylalkylidene, Cs-C8cycloalky- lene, C7-C8bicycloalkylene, unsubstituted or C,-C4alkyl-substituted phenylene, \ X2 is C2-C, 8alkylene, C4-C, 8alkylene which is interrupted by oxygen, sulfur or/N-Rl8 ; C2-C, Balkenylene, C5-C8Cycloalkylene, C7-C8bicycloalkylene, unsubstituted or C,-C4alkyl- substituted phenylen, \ X3 is C2-C, 8alkylene, C4-C18alkylene which is interrupted by oxygen, sulfur orN-R C2-C, 8alkenylene, Cs-C8cycloalkylene, C7-C8bicycloalkylene, unsubstituted or C,-C4alkyl- substituted phenylen, M is a metal cation of valency r, n is 1 or 2, p is 0, 1 or 2, q is 1, 2, 3, 4, 5 or 6, and r is 1, 2 or 3.

Alkanoyloxy having up to 25 carbon atoms is a branched or unbranched radical, for example formyloxy, acetoxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy, tridecanoyloxy, te- tradecanoyloxy, pentadecanoyloxy, hexadecanoyloxy, heptadecanoyloxy, octadecanoyloxy, icosanoyloxy or docosanoyloxy. Preference is given to alkanoyloxy having from 2 to 18, es- pecially from 2 to 12, e. g. from 2 to 6, carbon atoms. Special preference is given to acetoxy.

C3-C25AIkanoyloxy interrupted by oxygen, sulfur or by NR, 8 is, for example, CH3-O-CH2COO-, CH3-S-CH2COO-, CH3-N (CH3)-CH2COO-, CH3-O-CH2CH2-O-CH2COO-, CH3-(O-CH2CH2-)2O-CH2COO-, CH3-(O-CH2CH2-)3O-CH2COO- or CH3-(O-CH2CH2-)4O-CH2COO-.

C6-C9Cycloalkylcarbonyloxy is, for example, cyclopentylcarbonyloxy, cyclohexylcarbonyloxy, cycloheptylcarbonyloxy or cyclooctylcarbonyloxy. Preference is given to cyclohexylcarbonyl- oxy.

C3-C2sAIkenoyloxy interrupted by oxygen, sulfur or by # N-R18 is, for example, CH30CH2CH2CH=CHCOO-or CH30CH2CH20CH=CHCOO-.

C,-C, 2AIkyl-substituted benzoyloxy, which carries preferably from 1 to 3, especially 1 or 2, alkyl groups, is, for example, o-, m-or p-methylbenzoyloxy, 2, 3-dimethylbenzoyloxy, 2, 4-di- methylbenzoyloxy, 2, 5-dimethylbenzoyloxy, 2, 6-dimethylbenzoyloxy, 3, 4-dimethylbenzoyloxy, 3, 5-dimethylbenzoyloxy, 2-methyl-6-ethylbenzoyloxy, 4-tert-butylbenzoyloxy, 2-ethylbenzoyl- oxy, 2, 4, 6-trimethylbenzoyloxy, 2, 6-dimethyl-4-tert-butylbenzoyloxy or 3, 5-di-tert-butylbenz- oyloxy. Preferred substituents are C,-C8alkyl, especially C,-C4alkyl.

Alkyl having up to 25 carbon atoms is a branched or unbranched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1, 3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1, 1, 3, 3-tetra- methylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1, 1, 3-trimethylhexyl, 1, 1, 3, 3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1, 1, 3, 3, 5, 5- hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, icosyl or docosyl. One of the preferred definitions for R2 and R4 is, for example, C,-C, 8alkyl. An espe- cially preferred definition for R4 is C,-C4alkyl.

C3-C25AIkyl interrupted by oxygen, sulfur or by N-Ri, is, for example, CH3-O-CH2CH2- , CH3-S-CH2CH2-, CH3-N (CH3)-CH2CH2-, CH3-O-CH2CH2-O-CH2CH2-, CH3-(O-CH2CH2-) 2O-CH2CH2-, CH3-(O-CH2CH2-) 3O-CH2CH2-or CH3-(O-CH2CH2-04O-CH2CH2-.

Fluoro-substituted C,-C12alkyl is a branched or unbranched radical, for example fluorome- thyl, difluoromethyl, trifluoromethyl or pentafluoroethyl. Trifluoromethyl is preferred.

C7-CgPhenylalkyl is, for example, benzyl, a-methylbenzyl, a, a-dimethylbenzyl or 2-phenyl- ethyl. Preference is given to benzyl and a, a-dimethylbenzyl.

C7-CgPhenylalkyl unsubstituted or substituted on the phenyl radical by from 1 to 3 C1-C4alkyl groups is, for example, benzyl, a-methylbenzyl, a, a-dimethylbenzyl, 2-phenylethyl, 2-methyl- benzyl, 3-methylbenzyl, 4-methylbenzyl, 2, 4-dimethylbenzyl, 2, 6-dimethylbenzyl or 4-tert- butylbenzyl. Preference is given to benzyl.

C,-C4AIkyl-substituted phenyl, which contains preferably from 1 to 3, especially 1 or 2, alkyl groups, is, for example, o-, m-or p-methylphenyl, 2, 3-dimethylphenyl, 2, 4-dimethylphenyl, 2, 5-dimethyiphenyl, 2, 6-dimethylphenyl, 3, 4-dimethylphenyl, 3, 5-dimethylphenyl, 2-methyl-6- ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl or 2, 6-diethylphenyl.

Unsubstituted or C,-C4alkyl-substituted C5-CBcycloalkyl is, for example, cyclopentyl, methyl- cyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethyl- cyclohexyl, tert-butylcyclohexyl, cycloheptyl or cyclooctyl. Preference is given to cyclohexyl and tert-butylcyclohexyl.

Alkoxy having up to 18 carbon atoms is a branched or unbranched radical, for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentyloxy, isopentyloxy, hexyl- oxy, heptyloxy, octyloxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. Preference is given to alkoxy having from 1 to 12, especially from 1 to 8, e. g. from 1 to 6, carbon atoms.

Alkylthio having up to 18 carbon atoms is a branched or unbranched radical, for example methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, pentylthio, isopentyl- thio, hexylthio, heptylthio, octylthio, decylthio, tetradecylthio, hexadecylthio or octadecylthio.

Preference is given to alkylthio having from 1 to 12, especially from 1 to 8, e. g. from 1 to 6, carbon atoms.

Alkylamino having up to 4 carbon atoms is a branched or unbranched radical, for example methylamino, ethylamino, propylamino, isopropylamino, n-butylamino, isobutylamino or tert- butylamino.

Di (C,-C4alkyl) amino means also that the two radicals are each independently of the other branched or unbranched, for example, dimethylamino, methylethylamino, diethylamino, methyl-n-propylamino, methylisopropylamino, methyl-n-butylamino, methylisobutylamino, <BR> <BR> <BR> ethylisopropylamino, ethyl-n-butylamino, ethylisobutylamino, ethyl-tert-butylamino, diethyl- amino, diisopropylamino, isopropyl-n-butylamino, isopropylisobutylamino, di-n-butylamino or di-isobutylamino.

Alkanoylamino having up to 25 carbon atoms is a branched or unbranched radical, for example formylamino, acetylamino, propionylamino, butanoylamino, pentanoylamino, hexan- oylamino, heptanoylamino, octanoylamino, nonanoylamino, decanoylamino, undecanoyl- amino, dodecanoylamino, tridecanoylamino, tetradecanoylamino, pentadecanoylamino, hexadecanoylamino, heptadecanoylamino, octadecanoylamino, icosanoylamino or docosan- oylamino. Preference is given to alkanoylamino having from 2 to 18, especially from 2 to 12, e. g. from 2 to 6, carbon atoms.

C,-C, 8Alkylene is a branched or unbranched radical, for example methylene, ethylene, pro- pylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene or octadecamethylene. A preferred defi- nition for X, is C1-C, 2alkylene, especially C,-Csalkylene, for example C,-C8alkylene. A pre- ferred definition for X2 is C2-C18alkylene, especially C2-C8alkylene. A preferred definition for X3 is C2-C, 8alkylene, especially C2-C, 2alkylene, for example C4-C, 2alkylene.

C2-C, 8Alkylene interrupted by oxygen, sulfur or by NR8 is, for example, -CH2-0-CH2-,-CH2-S-CH2-,-CH2-N (CH3)-CH2-,-CH2-O-CH2CH2-,-CH2CH2-O-CH2CH2-, <BR> <BR> <BR> -CH2CH2-0-CH2CH2-0-CH2CH2-,-CH2CH2- (O-CH2CH2-) 20-CH2CH2-,<BR> <BR> <BR> <BR> -CH2CH2- (O-CH2CH2-) 30-CH2CH2-,-CH2CH2- (O-CH2CH2-) 40-CH2CH2- or<BR> <BR> <BR> <BR> -CH2CH2-S-CH2CH2-- Alkyliden having from 2 to 20 carbon atoms is, for example, ethylidene, propylidene, butyl- idene, pentylidene, 4-methylpentylidene, heptylidene, nonylidene, tridecylidene, nonadecyl- idene, 1-methylethylidene, 1-ethylpropylidene or 1-ethylpentylidene. Preference is given to C2-C8alkylidene.

Phenylalkylidene having from 7 to 20 carbon atoms is, for example, benzylidene, 2-phenyl- ethyliden or 1-phenyl-2-hexylidene. Preference is given to C7-C9phenylalkylidene.

C5-C8Cycloalkylene is a saturated hydrocarbon group having two free valences and at least one ring unit and is, for example, cyclopentylene, cyclohexylene, cycloheptylene or cyclo- octylene. Preference is given to cyclohexylene.

C7-C8Bicycloalkylene is, for example, bicycloheptylene or bicyclooctylene.

Phenylen or naphthylene each unsubstituted or substituted by C,-C4alkyl, fluoro, trifluoro- methyl or-CN is, for example, 1, 2-, 1, 3- or 1, 4-phenylene ; 1, 2-, 1, 3-, 1, 4-, 1, 6-, 1, 7-, 2, 6- or 2, 7-naphthylene ; 1, 4-(2-trifluormethyl) phenylene, 1, 4-(2-trifluormethyl) naphthylene or 1, 4- (2- cyano) phenylen.

A Cs-C8cycloalkylidene ring substituted by C,-C4alkyl, which contains preferably from 1 to 3, especially 1 or 2, branched or unbranched alkyl group radicals, is, for example, cyclopentyl- idene, methylcyclopentylidene, dimethylcyclopentylidene, cyclohexylidene, methylcyclohexyli- dene, dimethylcyclohexylidene, trimethylcyclohexylidene, tert-butylcyclohexylidene, cyclo- heptylidene or cyclooctylidene. Preference is given to cyclohexylidene and tert-butylcyclo- hexylidene.

A mono-, di-or tri-valent metal cation is preferably an alkali metal cation, alkaline earth metal cation or aluminium cation, for example Na+, K+, Mg++, Ca++ or Al+++.

Hydroxyl-substituted C2-C24alkyl is a branched or unbranched radical which contains prefe- rably 1 to 3, in particular 1 or 2, hydroxyl groups, such as, for example, hydroxyethyl, 3-hydr- oxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, 5-hydroxypentyl, 4-hydroxypentyl, 3-hydroxypentyl, 2-hydroxypentyl, 6-hydroxyhexyl, 5-hydroxyhexyl, 4- hydroxyhexyl, 3-hydroxyhexyl, 2-hydroxyhexyl, 7-hydroxyheptyl, 6-hydroxyheptyl, 5-hydroxy- heptyl, 4-hydroxyheptyl, 3-hydroxyheptyl, 2-hydroxyheptyl, 8-hydroxyoctyl, 7-hydroxyoctyl, 6- hydroxyoctyl, 5-hydroxyoctyl, 4-hydroxyoctyl, 3-hydroxyoctyl, 2-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 11-hydroxyundecyl, 12-hydroxydodecyl, 13-hydroxytridecyl, 14-hydroxytet- radecyl, 15-hydroxypentadecyl, 16-hydroxyhexadecyl, 17-hydroxyheptadecyl, 18-hydroxy- octadecyl, 20-hydroxyeicosyl or 22-hydroxydocosyl. A preferred definition of R24, R25, R27 and R28 is hydroxyl-substituted C4-C, 2alkyl, especially hydroxyl-substituted C5-C, 2alkyl, for example hydroxyl-substituted C5-C"alkyl. One of the preferred definitions of R24, R25 R27 and R28 is hydroxyl-substituted C2-C2oalkyl, especially hydroxyl-substituted C2-C, 8alkyl, for example hydroxyl-substituted C2-C, 4alkyl. A particularly preferred definition of R24, R25 R27 and R28 is hydroxyl-substituted C2-C, 2alkyl, especially hydroxyl-substituted C2-CBalkyl, for example hydroxyl-substituted C2-C4alkyl, such as 2-hydroxyethyl, for example.

Alkenyl having 3 to 24 carbon atoms is a branched or unbranched radical such as, for example, propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2, 4-pentadienyl, 3-methyl-2-butenyl, n- 2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Prefe- rence is given to alkenyl having 3 to 18, especially 3 to 12, for example 3 to 6, especially 3 to 4 carbon atoms.

Where R24 and R25 or R27 and R28, together with the nitrogen atom to which they are attached, form a 5-, 6-or 7-membered heterocyclic ring which is unsubstituted or is substituted by C,-C4alkyl or is interrupted by oxygen, sulfur or N-R18, this denotes, for example, the following radicals : R24 and R25 or R27 and R28 preferably form, with the nitrogen atom to which they are attached, a 6-membered heterocyclic ring interrupted by oxygen, such as, for example, Where R29 and R30, together with the nitrogen atom to which they are attached, form a 5-, 6- or 7-membered heterocyclic ring which is unsubstituted or is substituted by C,-C4alkyl or is interrupted by oxygen, sulfur or/N-R, 8, this denotes, for example, the following radi- cals : C2-C, 8Alkenylene is, for example, vinylene, methylvinylene, octenylethylene or dodecenyl- ethylene. C2-C8Alkenylene is preferred.

Preferred compounds of the formula I are those wherein, when n is 1, R, is a radical of the formula II, III or IV (")('")('v) and when n is 2, R2, R3, R4 and R5 are each independently of one another hydrogen, chloro, hydroxyl, C,-C, 8- alkyl, C7-C9phenylalkyl, phenyl, C5-C8cycloalkyl, C1-C18 alkoxy, C1-C18alkylthio, C1-C18alkano- yloxy, C1-C1 ealkanoylamino, C3-C, 8alkenoyloxy, C3-C, ealkanoyloxy which is interrupted by oxygen or sulfur ; C6-C9cycloalkylcarbonyloxy, benzoyloxy or C,-C4alkyl-substituted benzoyl- oxy ; or each pair of substituents R2 and R3 or R3 and R4 or R4 and R5 together with the lin- king carbon atoms, forms a benzene ring ; or R4 is additionally- (CH2) P-COR, g or- (CH2) qOH, or when R3, R5 and R6 are hydrogen, R4 is additionally a radical of the formula V (v) wherein R, is as defined above for n = 1, R6 is hydrogen or a radical of the formula VI (V!) in which R4 is not a radical of the formula V and R, is as defined above for n = 1, R7, R8, R9, R10, R11, R12, R13, R14 and R15 are each independently of one another hydrogen, fluoro, fluoro-substituted C,-Caalkyl ;-CN, -SOR26,-S02R26 or S03R26 ; with the proviso that at least one of R7, RB, Rg, R10, R11, R12, R13, R, 4 or R15 is not hydrogen, Rie and R17 are each independently of one another phenylen or naphthylene which are substituted by fluoro, trifluoromethyl,-CN, -SOR26,-S02R26 or S03R26, R18 is hydrogen or C,-C4alkyl, Rig is hydroxyl, C,-C, 8alkoxy or R20 and R2, are each independently of one another hydrogen, CF3, C1-C8alkyl or phenyl, or R20 and R2 together with the linking carbon atom, form a C5-CBcycloalkylidene ring ; R22 is hydrogen, hydroxyl, C,-C, 8alkyl, C7-Cgphenylalkyl, phenyl, C5-C8- cycloalkyl ; or C3-C25alkyl which is interrupted by oxygen or sulfur, R23 is C1-C22alkyl, C7-C9phenylalkyl, phenyl, C5-c8cycloalkyl or C3-C25alkyl which is inter- rupted by oxygen or sulfur, R24 and R25 are each independently of one another hydrogen, C,-C, 8alkyl, hydroxyl-substi- tuted C2-C, Balkyl ; C3-C18alkyl which is interrupted by oxygen, sulfur or N-R C7-C9- phenylalkyl, or C3-C, ealkenyl ; or R24 and R25, together with the nitrogen atom to which they are attached, form a 5-, 6-or 7-membered heterocyclic ring, R26 is hydrogen or C1-C18alkyl, R27 and R28 are each independently of one another hydrogen, C1-C18alkyl, hydroxyl-substi- tuted C2-C, 8alkyl ; C3-C18alkyl which is interrupted by oxygen, su)furorN-Fg;67-09- phenylalkyl, or C3-C18 alkenyl; or R27 and R28, together with the nitrogen atom to which they are attached, form a 5-, 6-or 7-membered heterocyclic ring, R29 and R30 are each independently of one another hydrogen, C,-C, 8alkyl or C7-C9phenyl- alkyl, or R29 and R30 together with the nitrogen atom to which they are attached form a 5-, 6- or 7-membered heterocyclic ring, X, is a direct bond, C,-C, 2alkylene, C2-C, 8alkylene which is interrupted by oxygen or sulfur ; <BR> <BR> C2-C, 2alkenylene, C2-C, 2alkylidene, C7-C,2phenylalkylidene, C5-C8cycloalkylene, phenylene, X2 is C2-C12alkylene, C4-C12alkylene which is interrupted by oxygen, sulfur or # N-R18 ; C2-C, 2alkenylene, C5-C8cycloalkylene, phenylene, X3 is C2-C18alkylene, C4-C12alkylene which is interrupted by oxygen, sulfur or # N-R18 ; C2-C, 2alkenylene, C5-C8cycloalkylene, phenylene, M is a metal cation of valency r, n is 1 or 2, p is 0, 1 or 2, q is 1, 2, 3, 4, 5 or 6, and r is 1, 2 or 3.

Further preferred compounds of the formula i are those wherein, when n is 1, R, is a radical of the formula II, III or IV, and when n is 2, R, is R2, R3, R4 and R5 are each independently of one another hydrogen, C,-C, 8alkyl, C7-Cgphe- nylalkyl, phenyl, cyclohexyl, C1-C12alkoxy, C1-C12alkylthio, C1-C12alkanoyloxy, C3-C12alkenoyl- oxy, C3-C, 2alkanoyloxy which is interrupted by oxygen ; cyclohexylcarbonyloxy, benzoyloxy or each pair of substituents R2 and R3 or R3 and R4 or R4 and R5 together with the linking carbon atoms, forms a benzene ring ; or R4 is additionally -(CH2)p-COR19, or -(CH2)qOH, or when R3, R5 and R6 are hydrogen, R4 is additionally a radical of the formula V, wherein R, is as defined above for n = 1, R6 is hydrogen or a radical of the formula VI in which R4 is not a radical of the formula V and R, is as defined above for n = 1, R7, R8, Rg, R, o, R", R, 2, R, 3, R, 4 and R, 5 are each independently of one another hydrogen, fluoro, fluoro-substituted C,-C4alkyl ;-CN, -SOR26,-S02R26 or SOsRse ; with the proviso that at least one of R7, R8, Rg, R, o, R", R, 2, R, 3, R, 4 or R, 5 is not hydrogen, R, 6 and R17 are each independently of one another phenylen or naphthylene, Rig is hydroxyl, C1-C18alkoxy or R20 and R2, are each independently of one another hydrogen, CF3 or C,-C4alkyl, or R20 and R2, together with the linking carbon atom, form a cyclohexylidene ring ; R22 is hydroxyl, C1-C12alkyl, phenyl, cyclohexyl or C3-C12alkyl which is interrupted by oxygen, R23 is C,-C22alkyl, benzyl, phenyl, cyclohexyl or C3-C, 2alkyl which is interrupted by oxygen, R24 and R25 are each independently of one another hydrogen, C,-C, 2alkyl, hydroxyl-substitu- ted C2-C12 alkyl ; C3-C, 2alkyl which is interrupted by oxygen ; benzyl or C3-C12 alkenyl ; or R24 and R25, together with the nitrogen atom to which they are attached, form 6-membered hete- rocyclic ring, R26 is C,-C, 2alkyl, R27 and R28 are each independently of one another hydrogen, C,-C, 2alkyl, hydroxyl-substitu- ted C2-C12alkyl ; C3-C, 8alkyl which is interrupted by oxygen ; benzyl or C3-C12alkenyl ; or R27 and R28, together with the nitrogen atom to which they are attached, form 6-membered hete- rocyclic ring, R29 and R30 are each independently of one another hydrogen, C,-C, 2alkyl or benzyl, or R29 and R30 together with the nitrogen atom to which they are attached form a 6-membered hete- rocyclic ring, X, is a direct bond, C1-C8alkylene, C2-C, 8alkylene which is interrupted by oxygen ; pheny- lene, X2 is C2-C8alkylene, C4-C, 2alkylene which is interrupted by oxygen ; cyclohexylene, pheny- lene, X3 is C2-C18alkylene, C4-C12alkylene which is interrupted by oxygen ; C2-C, 2alkenylene, cyclo- hexylen, phenylen, n is 1 or 2, p is 1 or 2, and q is 2 or 3.

Also preferred are compounds of the formula I wherein, when n is 1, R, is a radical of the formula II, and when n is 2, R2 is hydrogen, C,-C, Balkyl, C7-Cgphenylalkyl, phenyl, cyclohexyl, C,-Cealkanoyloxy or benzoyloxy, R3 is hydrogen or C,-C4alkyl, R4 is hydrogen, C1-C18alkyl, C7-C9phenylalkyl, phenyl, cyclohexyl, C1-C8alkanoyloxy, - (CH2) p-COR,9 or- (CH2) qOH, or when R3, R5 and R6 are hydrogen, R4 is additionally a radical of the formula V, wherein R, is as defined above for n = 1, R5 is hydrogen or C,-C4alkyl, R6 is hydrogen or a radical of the formula Vi in which R4 is not a radical of the formula V and R, is as defined above for n = 1, R7, R8, Rg, Rio and R11 are each independently of one another hydrogen, fluoro, fluoro-sub- stituted C,-C4alkyl ;-CN, -SOR26, or SO2R26 ; with the proviso that at least one of R7, R8, Rg, Rio or R"is not hydrogen, R, 6 and R17 are each independently of one another phenylen or naphthylene, Rig is Ci-Cgatkoxy, R20 and R2, are each independently of one another hydrogen, CF3 or C,-C4alkyl, or R20 and R2, together with the linking carbon atom, form a cyclohexylidene ring ; R23 is C,-C22alkyl, benzyl, phenyl, cyclohexyl or C3-C12alkyl which is interrupted by oxygen, R24 and R25 are each independently of one another hydrogen, C,-C4alkyl, hydroxyl-substitu- ted C2-C4alkyl ; C3-C, 2alkyl which is interrupted by oxygen ; benzyl or C3-C, 2alkenyl, R26 is C1-C8alkyl, R29 and R30 are each independently of one another hydrogen, C1-C8alkyl or benzyl, X, is a direct bond, C1-C8alkylene, X2 is C2-C8alkylene or C4-C12alkylene which is interrupted by oxygen, X3 is C2-C, 8alkylene or C4-C12alkylene which is interrupted by oxygen, n is 1 or 2, p is 1 or 2, and q is2or3.

Particularly interesting compounds of the formula I are those wherein, when n is 1, R, is a radical of the formula 11, and when n is 2, R2 is C1-C18alkyl, C7-C9phenylalkyl, phenyl or cyclohexyl, R3 is hydrogen or methyl, R4 is hydrogen, C1-C18alkyl, C7-C9phenylalkyl, phenylo, cyclohexyl or a radical of the formula V, wherein R, is as defined above for n = 1, R5 is hydrogen or methyl, R6 is hydrogen or a radical of the formula VI in which R4 is not a radical of the formula V and R, is as defined above for n = 1, R7, R8, R9 R10 and R"are each independently of one another hydrogen, fluoro, fluoro-sub- stituted C,-C4alkyl ;-CN, -SOR26, or-S02R26 ; with the proviso that at least one of R7, R8, R9, R10 or R"is not hydrogen, R, 6 and R17 are each independently of one another phenylen or naphthylene, R20 and R2, are each independently of one another hydrogen or C,-C4alkyl, or R2o and R2, together with the linking carbon atom, form a cyclohexylidene ring ; R23 is C,-C22alkyl, benzyl, phenyl, cyclohexyl or C3-C, 2alkyl which is interrupted by oxygen, R26 is C,-C8alkyl, X, is a direct bond, C1-C8alkylene or-O-X3 O-, X3 is C2-C, Balkylene or C4-Cl2alkylene which is interrupted by oxygen, and n is 1 or 2.

Compounds of the formula I of very particular interest are those wherein, when n is 1, R, is a radical of the formula II, and when n is 2, R2 is C,-C8alkyl or cyclohexyl, R3 is hydrogen, R4 is hydrogen, C1-C8alkyl, cyclohexyl or a radical of the formula V, wherein R, is as defined above for n = 1, R5 is hydrogen, R6 is hydrogen or a radical of the formula VI in which R4 is not a radical of the formula V and R, is as defined above for n = 1, R7, R8, Rg, Rio and R"are each independently of one another hydrogen, fluoro, trifluor- methyl ;-CN or with the proviso that at least one of R7, R8, Rg, Rio or Rn is not hydrogen, R16 and R17 are each independently of one another phenylen or naphthylene, R20 and R2, are each independently of one another hydrogen or C1-C4alkyl, or R2o and R2, together with the linking carbon atom, form a cyclohexylidene ring ; R23 is C1-C22alkyl, benzyl or cyclohexyl, X, is C,-C8alkylene or-O-X3 O-, X3 is C2-C, 4alkylene, and n is 1 or 2.

Very particularly preferred compounds of the formula I are those wherein when n is 1, R, is a radical of the formula II, and when n is 2, R2 is C,-C4alkyl, R3 is hydrogen, R4 is C,-C4alkyl, R5 is hydrogen, R6 is hydrogen or a radical of the formula VI wherein R, is as defined above for n = 1, R7 is hydrogen or trifluoromethyl, R8 is hydrogen, trifluoromethyl or-CN, Rg is hydrogen or trifluoromethyl, Rio is hydrogen, trifluoromethyl or-CN, Ril is hydrogen, fluoro, trifluoromethyl,-CN or with the proviso that at least one of R7, R8, Rg, Rio or R"is not hydrogen, R, 6 and Ru are phenytene or naphthylene, R23 is C,-C22alkyl, X, is-O-X3 O-, X3 is C4-Cr2alkylene, and n is 1 or 2.

The compounds of the formula I can be prepared in per se known manner. A preferred pro- cess for the preparation of the compounds of the formula I is disclosed in WO-A-99/67232.

The compounds of the formula I are suitable for stabilizing organic materials against oxi- dative, thermal or light-induced degradation. Special attention is drawn to their excellent action as antioxidants in the stabilization of organic materials.

Illustrative examples of such materials are : 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, po- lybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, i. e. the polymers of monoolefins exemplified in the preceding paragraph, prefe- rably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods : a) radical polymerisation (normally under high pressure and at elevated temperature). b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either it-or c-coordinated.

These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium (ill) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, Ila and/or Illa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Philips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copo- lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e. g. ethylene/norbornene like COC), ethylene/1-olefins copolymers, where the 1-olefin is gene- rated in-situ ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vi- nylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene ; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethy- lene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene- acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyal- kylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (e. g. tackifiers) and mixtures of polyalkylenes and starch.

Homopolymers and copolymers from 1.)-4.) may have any stereostructure including syndio- tactic, isotactic, hemi-isotactic or atactic ; where atactic polymers are preferred. Stereoblock polymers are also included.

5. Polystyrene, poly (p-methylstyrene), poly (a-methylstyrene).

6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers including styrene, a-methylstyrene, all isomers of vinyl toluene, especially p-vinyltoluene, all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, and mixtures thereof. Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic ; where atactic polymers are preferred. Ste- reoblock polymers are also included.

6a. Copolymers including aforementioned vinyl aromatic monomers and comonomers selec- ted from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/bu- tadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhy- dride, styrene/acrylonitrile/methyl acrylate ; mixtures of high impact strength of styrene copo- lymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/pro- pylene/diene terpolymer ; and block copolymers of styrene such as styrene/butadiene/sty- rene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propy- lene/styrene.

6b. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6.), especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).

6c. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6a.).

Homopolymers and copolymers may have any stereostructure including syndiotactic, isotac- tic, hemi-isotactic or atactic ; where atactic polymers are preferred. Stereoblock polymers are also included.

7. Graft copolymers of vinyl aromatic monomers such as styrene or a-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acry- lonitrile copolymers ; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene ; styrene, acrylonitrile and methyl methacrylate on polybutadiene ; styrene and maleic anhydride on polybutadiene ; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene ; styrene and maleimide on polybutadiene ; styrene and alkyl acrylates or methacrylates on polybutadiene ; styrene and acrylonitrile on ethylene/propylene/diene terpolymers ; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo- chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo-and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from a, 5-unsaturated acids and derivatives thereof such as polyacry- lates and polymethacrylates ; polymethyl methacrylates, polyacrylamides and polyacryloni- triles, impact-modified with butyl acrylate.

10. Copolymers of the monomers mentioned under 9) with each other or with other unsatu- rated monomers, for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acry- lonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or ace- tals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine ; as well as their copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethy- lene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer ; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadi- enes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid ; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an ela- stomer as modifier, for example poly-2, 4, 4,-trimethylhexamethylene terephthalamide or poly- m-phenylene isophthalamide ; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers ; or with polyethers, e. g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol ; as well as polyamides or copolyamides modified with EPDM or ABS ; and polyamides condensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene tereph- thalate, poly-1, 4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers ; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde re- sins and melamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acry- lates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e. g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.

27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose ; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6. 6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

29. Naturally occurring and synthetic organic materials which are pure monomeric com- pounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e. g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, e. g. natural latex or latices of carbo- xylated styrene/butadiene copolymers.

Further objects of the invention are therefore compositions comprising a) an organic material that is susceptible to oxidative, thermal or light-induced degradation, and b) at least one compound of the formula I.

Preferred organic materials are natural, semi-synthetic or, preferably, synthetic polymers.

Particularly referred organic materials are synthetic polymers, most preferably thermoplastic polymers. Especially preferred organic materials are polyacetals, polyolefins such as poly- propylene or polyethylene, polyether/polyurethanes, polyesters such as polybutylene tereph- thalate, polycarbonates or vulcanisates, To be singled out for special mention is the efficacy of the novel compounds of the formula I against oxidative or thermal degradation, especially under the action of heat which occurs during the processing of thermoplasts. The compounds of the formula I of this invention are therefore admirably suited for use as processing stabilizers.

The compounds of the formula I will preferably be added to the organic material to be stabi- lized in concentrations of 0. 0005 to 10 %, preferably 0. 001 to 2 %, typically 0. 01 to 2 %, based on the weight of said material.

In addition to comprising the compounds of the formula 1, the inventive compositions may comprise further co-stabilizers, typically the following : 1. Antioxidants 1. 1. Atkvtated monophenols, for example 2, 6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4, 6-di- methylphenol, 2, 6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-n-butylphenol, 2, 6-di-tert-bu- tyl-4-isobutylphenol, 2, 6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4, 6-dimethyl- phenol, 2, 6-dioctadecyl-4-methylphenol, 2, 4, 6-tricyclohexylphenol, 2, 6-di-tert-butyl-4-meth- oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2, 6-di-nonyl-4-methylphenol, 2, 4-dimethyl-6- (1'-methylundec-1'-yl) phenol, 2, 4-dimethyl-6- (1'- methylheptadec-1'-yl) phenol, 2, 4-dimethyl-6- (1'-methyltridec-1'-yl) phenol and mixtures there- of.

1. 2. AlkvlthiomethvlPhenolsR for example 2, 4-dioctylthiomethyl-6-tert-butylphenol, 2, 4-dioctyl- thiomethyl-6-methylphenol, 2, 4-dioctylthiomethyl-6-ethylphenol, 2, 6-di-dodecylthiomethyl-4- nonylphenol.

1. 3. Hydroquinones and alkylated hydroquinones, for example 2, 6-di-tert-butyl-4-methoxy- phenol, 2, 5-di-tert-butylhydroquinone, 2, 5-di-tert-amylhydroquinone, 2, 6-diphenyl-4-octade- cyloxyphenol, 2, 6-di-tert-butylhydroquinone, 2, 5-di-tert-butyl-4-hydroxyanisole, 3, 5-di-tert-bu- tyl-4-hydroxyanisole, 3, 5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3, 5-di-tert-butyl-4-hy- droxyphenyl) adipate.

1. 4. Tocopherols, for example a-tocopherol, 0-tocopherol, y-tocopherol, 8-tocopherol and mixtures thereof (vitamin E).

1. 5. Hydroxvlated thiodiphenyl ethers, for example 2, 2'-thiobis (6-tert-butyl-4-methylphenol), 2, 2'-thiobis (4-octylphenol), 4, 4'-thiobis (6-tert-butyl-3-methylphenol), 4, 4'-thiobis (6-tert-butyl- 2-methylphenol), 4, 4'-thiobis (3, 6-di-sec-amylphenol), 4, 4'-bis (2, 6-dimethyl-4-hydroxyphenyl)- disulfide.

1. 6. Alkvlidenebisphenols, for example 2, 2'-methylenebis (6-tert-butyl-4-methylphenol), 2, 2'- methylenebis (6-tert-butyl-4-ethylphenol), 2, 2'-methylenebis [4-methyl-6- (a-methylcyclohexyl)- phenol], 2, 2'-methylenebis (4-methyl-6-cyclohexylphenol), 2, 2'-methylenebis (6-nonyl-4- methylphenol), 2, 2'-methylenebis (4, 6-di-tert-butylphenol), 2, 2'-ethylidenebis (4, 6-di-tert-butyl- phenol), 2, 2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2, 2'-methylenebis [6- (a-methylben- zyl)-4-nonylphenol], 2, 2'-methylenebis [6-(a, a-dimethylbenzyl)-4-nonylphenol], 4, 4'-methy- lenebis (2, 6-di-tert-butylphenol), 4, 4'-methylenebis (6-tert-butyl-2-methylphenol), 1, 1-bis (5- tert-butyl-4-hydroxy-2-methylphenyl) butane, 2, 6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl)-4- methylphenol, 1, 1, 3-tris (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, 3-bis (3'-tert- butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methyl-phenyl) dicyclopenta- diene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-me thylphenyl] terephtha- late, 1, 1-bis- (3, 5-dimethyl-2-hydroxyphenyl) butane, 2, 2-bis (3, 5-di-tert-butyl-4-hydroxyphe- nyl) propane, 2, 2-bis- (5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobu tane, 1, 1, 5, 5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.

1. 7. O-N-and S-benzvl compounds, for example 3, 5, 3', 5'-tetra-tert-butyl-4, 4'-dihydroxydi- benzyl ether, octadecyl-4-hydroxy-3, 5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy- 3, 5-di-tert-butylbenzylmercaptoacetate, tris (3, 5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4- tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) dithioterephthalate, bis (3, 5-di-tert-butyl-4-hydroxy- benzyl) sulfide, isooctyl-3, 5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1. 8. Hvdroxybenzvlated malonate, for example dioctadecyl-2, 2-bis (3, 5-di-tert-butyl-2-hy- droxybenzyl) malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, di- dodecylmercaptoethyl-2, 2-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1, 1, 3, 3-te- tramethylbutyl) phenyl]-2, 2-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) malonate.

1. 9. Aromatic hydroxvbenzyl compounds, for example 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxy- benzyl)-2, 4, 6-trimethylbenzene, 1, 4-bis (3, 5-di-tert-butyl-4-hydroxybenzyl)-2, 3, 5, 6-tetrame- thylbenzene, 2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) phenol.

1. 10. Triazine compounds, for example 2, 4-bis (octylmercapto)-6- (3, 5-di-tert-butyl-4-hydroxy- anilino)-1, 3, 5-triazine, 2-octylmercapto-4, 6-bis (3, 5-di-tert-butyl-4-hydroxyanilino)-1, 3, 5-tri- azine, 2-octylmercapto-4, 6-bis (3, 5-di-tert-butyl-4-hydroxyphenoxy)-1, 3, 5-triazine, 2, 4, 6-tris- (3, 5-di-tert-butyl-4-hydroxyphenoxy)-1, 2, 3-triazine, 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxyben- zyl) isocyanurate, 1, 3, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate, 2, 4, 6-tris- (3, 5-di-tert-butyl-4-hydroxyphenylethyl)-1, 3, 5-triazine, 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxy- phenylpropionyl)-hexahydro-1, 3, 5-triazine, 1, 3, 5-tris (3, 5-dicyclohexyl-4-hydroxybenzyl) iso- cyanurate.

1. 11. Benzvlphosphonates, for example dimethyl-2, 5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3, 5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate , the calcium salt of the monoethyl ester of 3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1. 12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3, 5-di-tert-butyl-4-hydroxyphenyl) carbamate.

1. 13. Esters of ß-(3, 5-di-tert-butvl-4-hvdroxvphenyl) propionic acid with mono-or polyhydric alcohols, e. g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1, 6-hexanediol, 1, 9- nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy- lene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hy- droxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol- propane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2. 2. 2] octane.

1. 14. Esters of 3- (5-tert-butyl-4-hydroxv-3-methylphenvl) propionic acid with mono-or poly- hydric alcohols, e. g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1, 6-hexanedi- ol, 1, 9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis- (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyl- propane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2. 2. 2] octane ; 3, 9-bis [2- {3- (3-tert- butyl-4-hydroxy-5-methylphenyl) propionyloxy}-1, 1-dimethylethyl]-2, 4, 8, 10-tetraoxaspiro [5. 5]- undecane.

1. 15. Esters of S-(3, 5-dicvclohexvl-4-hvdroxyphenyl) proPionic acid with mono-or polyhydric alcohols, e. g. with methanol, ethanol, octanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, tri- ethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2. 2. 2] octane.

1. 16. Esters of 3, 5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alco- hols, e. g. with methanol, ethanol, octanol, octadecanol, 1, 6-hexanediol, 1, 9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2. 2. 2] octane.

1. 17. Amides of ß-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e. g. N, N'-bis (3, 5-di-tert- butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N'-bis (3, 5-di-tert-butyl-4-hydroxy- phenylpropionyl) trimethylenediamide, N, N'-bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hy- drazide, N, N'-bis [2- (3- [3, 5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (Nau- gard@XL-1, supplied by Uniroyal).

1. 18. Ascorbic acid (vitamin C) 1. 19. Aminic antioxidants, for example N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-bu- tyl-p-phenylenediamine, N, N'-bis (1, 4-dimethylpentyl)-p-phenylenediamine, N, N'-bis (1-ethyl-3- methylpentyl)-p-phenylenediamine, N, N'-bis (1-methylheptyl)-p-phenylenediamine, N, N'-dicy- clohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl)-p- phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl)-N'-phe-<BR> nyl-p-phenylenediamine, N- (1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'- phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl-N, N'-di- sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenyl- amine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naph- thylamine, octylated diphenylamine, for example p, p'-di-tert-octyldiphenylamine, 4-n-butyl- aminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4- octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2, 6-di-tert-butyl-4-dimethylamino- methylphenol, 2, 4'-diaminodiphenylmethane, 4, 4'-diaminodiphenyl methane, N, N, N', N'-tetra- methyl-4, 4'-diaminodiphenylmethane, 1, 2-bis [(2-methylphenyl) amino] ethane, 1, 2-bis (phenyl- amino) propane, (o-tolyl) biguanide, bis [4-(1',3'-dimethylbutyl)phenyl] amine, tert-octylated N- phenyl-1-naphthylamine, a mixture of mono-and dialkylated tert-butyl/tert-octyldiphenyl- amines, a mixture of mono-and dialkylated nonyldiphenylamines, a mixture of mono-and dialkylated dodecyldiphenylamines, a mixture of mono-and dialkylated isopropyl/isohexyl- diphenylamines, a mixture of mono-and dialkylated tert-butyldiphenylamines, 2, 3-dihydro- 3, 3-dimethyl-4H-1, 4-benzothiazine, phenothiazine, a mixture of mono-and dialkylated tert- butyl/tert-octylphenothiazines, a mixture of mono-and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N, N, N', N'-tetraphenyl-1, 4-diaminobut-2-ene, N, N-bis (2, 2, 6, 6-tetra- methylpiperid-4-yl-hexamethylenediamine, bis (2, 2, 6, 6-tetramethylpiperid-4-yl) sebacate, 2, 2, 6, 6-tetramethylpiperidin-4-one, 2, 2, 6, 6-tetramethylpiperidin-4-ol.

2. UV absorbers and liqht stabilizers 2. 1. 2- (2'-Hydroxypheny benzotriazoles, for example 2- (2'-hydroxy-5'-methylphenyl) benzo- <BR> <BR> <BR> triazole, 2- (3', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphe- nyl) benzotriazole, 2- (2'-hydroxy-5'- (1, 1, 3, 3-tetramethylbutyl)phenyl)benzotriazole, 2-(3', 5'-di- <BR> <BR> <BR> tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphe-<BR> <BR> <BR> <BR> nyl)-5-chlorobenzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-<BR> <BR> <BR> <BR> hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole,<BR> <BR> <BR> <BR> 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotri azole, 2-(3'-tert-butyl-2'-hydroxy-5'-<BR> <BR> <BR> <BR> (2-octyloxycarbonylethyl) phenyl)-5-chlorobenzotriazole, 2- (3'-tert-butyl-5'- [2- (2-ethylhexyl- oxy) carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2- <BR> <BR> <BR> methoxycarbonylethyl) phenyl)-5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2-meth-<BR> <BR> <BR> <BR> oxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2-octyloxycarbonyl-<BR> <BR> <BR> <BR> ethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5'- [2- (2-ethylhexyloxy) carbonyl ethyl]-2'-hydroxy-<BR> <BR> <BR> <BR> phenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl- 2'-hydroxy-5'- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2, 2'-methylenebis [4- (1, 1, 3, 3- tetramethylbutyl)-6-benzotriazole-2-ylphenol] ; the transesterification product of 2- [3'-tert-bu- tyl-5'- (2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300 ; [R-CH2CH2 COO-CH2CH2, where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotri- 2 azol-2-ylphenyl, 2- [2'-hydroxy-3'- (a, a-dimethylbenzyl)-5'- (1, 1, 3, 3-tetramethylbutyl) phenyl]- benzotriazole ; 2- [2'-hydroxy-3'- (1, 1, 3, 3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)phenyl] ben- zotriazole.

2. 2. 2-Hydroxvbenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl- oxy, 4-dodecyloxy, 4-benzyloxy, 4, 2', 4'-trihydroxy and 2'-hydroxy-4, 4'-dimethoxy derivatives.

2. 3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylben- zoyl) resorcinol, benzoyl resorcinol, 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzo- ate, hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3, 5-di-tert-butyl-4-hydroxyben- zoate, 2-methyl-4, 6-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate.

2. 4. Acrylates, for example ethyl a-cyano-ß, ß-diphenylacrylate, isooctyl a-cyano-ß, ß-diphe- nylacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-p-methyl-p-methoxycinna- mate, butyl a-cyano-p-methyl-p-methoxycinnamate, methyl a-carbomethoxy-p-methoxycin- namate and N-(ß-carbomethoxy-ß-cyanovinyl)-2-methylindoline.

2. 5. Nickel compounds, for example nickel complexes of 2, 2'-thiobis [4- (1, 1, 3, 3-tetramethyl- butyl) phenol], such as the 1 : 1 or 1 : 2 complex, with or without additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyidithiocarbamate, nickel salts of the monoalkyl esters, e. g. the methyl or ethyl ester, of 4-hydroxy-3, 5-di-tert- butylbenzylphosphonic acid, nickel complexes of ketoximes, e. g. of 2-hydroxy-4-methylphe- nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or with- out additional ligands.

2. 6. Sterically hindered amines, for example bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, bis (2, 2, 6, 6-tetramethyl-4-piperidyl) succinate, bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, bis (1, 2, 2, 6, 6-pentamethyl-4-piperi- dyl) n-butyl-3, 5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1- (2-hydroxyethyl)- 2, 2, 6, 6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N, N'-bis (2, 2, 6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2, 6-di- chloro-1, 3, 5-triazine, tris (2, 2, 6, 6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2, 2, 6, 6-tetra- methyl-4-piperidyl)-1, 2, 3, 4-butanetetracarboxylate, 1, 1'- (1, 2-ethanediyl)-bis (3, 3, 5, 5-tetrame- thylpiperazinone), 4-benzoyl-2, 2, 6, 6-tetramethylpiperidine, 4-stearyloxy-2, 2, 6, 6-tetramethyl- piperidine, bis (1, 2, 2, 6, 6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3, 5-di-tert-butylbenzyl)- malonate, 3-n-octyl-7, 7, 9, 9-tetramethyl-1, 3, 8-triazaspiro [4. 5] decane-2, 4-dione, bis (1-octyl- oxy-2, 2, 6, 6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2, 2, 6, 6-tetramethylpiperidyl) succi- nate, linear or cyclic condensates of N, N'-bis (2, 2, 6, 6-tetramethyl-4-piperidyl) hexamethylene- diamine and 4-morpholino-2, 6-dichloro-1, 3, 5-triazine, the condensate of 2-chloro-4, 6-bis (4-n- butylamino-2, 2, 6, 6-tetramethylpiperidyl)-1, 3, 5-triazine and 1, 2-bis (3-aminopropylamino)- ethane, the condensate of 2-chloro-4, 6-di- (4-n-butylamino-1, 2, 2, 6, 6-pentamethylpiperidyl)- 1, 3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7, 7, 9, 9-tetrame- thyl-1, 3, 8-triazaspiro [4. 5] decane-2, 4-dione, 3-dodecyl-1-(2, 2, 6, 6-tetramethyl-4-piperidyl) pyr- rolidine-2, 5-dione, 3-dodecyl-1- (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) pyrrolidine-2, 5-dione, a mixture of 4-hexadecyloxy-and 4-stearyloxy-2, 2, 6, 6-tetramethylpiperidine, a condensate of N, N'-bis (2, 2, 6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2, 6- dichloro-1, 3, 5-triazine, a condensate of 1, 2-bis (3-aminopropylamino) ethane and 2, 4, 6-tri- chloro-1, 3, 5-triazine as well as 4-butylamino-2, 2, 6, 6-tetramethylpiperidine (CAS Reg. No.

[136504-96-6]) ; a condensate of 1, 6-hexanediamine and 2, 4, 6-trichloro-1, 3, 5-triazine as well as N, N-dibutylamine and 4-butylamino-2, 2, 6, 6-tetramethylpiperidine (CAS Reg. No.

[192268-64-7]) ; N- (2, 2, 6, 6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide, N- (1, 2, 2, 6, 6- pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7, 7, 9, 9-tetramethyl-1-oxa-3, 8-di- aza-4-oxo-spiro [4, 5] decane, a reaction product of 7, 7, 9, 9-tetramethyl-2-cycloundecyl-1-oxa- 3, 8-diaza-4-oxospiro- [4, 5] decane and epichlorohydrin, 1, 1-bis (1, 2, 2, 6, 6-pentamethyl-4- piperidyloxycarbonyl)-2- (4-methoxyphenyl) ethene, N, N'-bis-formyl-N, N'-bis (2, 2, 6, 6-tetrame- thyl-4-piperidyl) hexamethylenediamine, a diester of 4-methoxymethylenemalonic acid with 1, 2, 2, 6, 6-pentamenthyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4(2, 2, 6, 6-tetramethyl-4- piperidyl)] siloxane, a reaction product of maleic acid anhydride-a-olefin copolymer with 2, 2, 6, 6-tetramethyl-4-aminopiperidine or 1, 2, 2, 6, 6-pentamethyl-4-aminopiperidine.

2. 7. Oxamides, for example 4, 4'-dioctyloxyoxanilide, 2, 2'-diethoxyoxanilide, 2, 2'-dioctyloxy- 5, 5'-di-tert-butoxanilide, 2, 2'-didodecyloxy-5, 5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5, 4'-di-tert-butoxanilide, mixtures of o-and p-methoxy-disubstituted oxanilides and mixtures of o-and p-ethoxy-disubstituted oxanilides.

2. 8. 2- (2-Hydroxyphenvl)-1, 3. 5-triazines, for example 2, 4, 6-tris (2-hydroxy-4-octyloxyphenyl)- 1, 3, 5-triazine, 2- (2-hydroxy-4-octyloxyphenyl)-4, 6-bis (2, 4-dimethylphenyl)-1, 3, 5-triazine, 2- (2, 4-dihydroxyphenyl)-4, 6-bis (2, 4-dimethylphenyl)-1, 3, 5-triazine, 2, 4-bis (2-hydroxy-4-propyl- oxyphenyl)-6-(2, 4-dimethylphenyl)-1, 3, 5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4, 6-bis (4- methylphenyl)-1, 3, 5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4, 6-bis (2, 4-dimethylphenyl)- 1, 3, 5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl)-4, 6-bis (2, 4-dimethylphenyl)-1, 3, 5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl]-4, 6-bis (2, 4-dimethyl)-1, 3, 5-triazine, 2- [2- hydroxy-4-(2-hydroxy-3-octyloxypropyloxy) phenyl]-4, 6-bis (2, 4-dimethyl)-1, 3, 5-triazine, 2- [4- (dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4 , 6-bis (2, 4-dimethylphenyl)- 1, 3, 5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy) phenyl]-4, 6-bis (2, 4-dimethyl- phenyl)-1, 3, 5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4, 6-diphenyl-1, 3, 5-triazine, 2- (2-hy- droxy-4-methoxyphenyl)-4, 6-diphenyl-1, 3, 5-triazine, 2, 4, 6-tris [2-hydroxy-4- (3-butoxy-2-hy- droxypropoxy) phenyl]-1, 3, 5-triazine, 2- (2-hydroxyphenyl)-4- (4-methoxyphenyl)-6-phenyl- 1, 3, 5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-oxy)-2-hydroxypropyloxy] phenyl}-4, 6-bis (2, 4- dimethylphenyl)-1, 3, 5-triazine.

3. Metal deactivators, for example N, N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2, 4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N, N'-diacetyladipoyl dihydrazide, N, N'-bis (salicyl- oyl) oxalyl dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyidialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phos- phite, distearylpentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 4-di- cumylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2, 4-di-tert-butyl-6-methylphenyl)- pentaerythritol diphosphite, bis (2, 4, 6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristea- ryl sorbitol triphosphite, tetrakis (2, 4-di-tert-butylphenyl) 4, 4'-biphenylene diphosphonite, 6- isooctyloxy-2, 4, 8, 1 0-tetra-tert-butyl-1 2H-dibenz [d, g]-1, 3, 2-dioxaphosphocin, bis (2, 4-di-tert- butyl-6-methylphenyl) methyl phosphite, bis (2, 4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 6-fluoro-2, 4, 8, 10-tetra-tert-butyl-12-methyl-dibenz [d, g]-1, 3, 2-dioxaphosphocin, 2, 2', 2"-nitrilo- [triethyltris (3, 3', 5, 5'-tetra-tert-butyl-1, 1'-biphenyl-2, 2'-diyl) phosphite], 2-ethylhexyl (3, 3', 5, 5'-te- tra-tert-butyl-1, 1'-biphenyl-2, 2'-diyl) phosphite, 5-butyl-5-ethyl-2- (2, 4, 6-tri-tert-butylphenoxy)- 1, 3, 2-dioxaphosphirane.

5. Hvdroxvlamines, for example N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N- dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N- dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydrox- ylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated tallow amine.

6. Nitrones, for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methyinitrone, N-octyl- alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N- hexadecyl-alpha-pentadecyinitrone, N-octadecyl-alpha-heptadecyinitrone, N-hexadecyl-al-<BR> pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta- decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N, N-dialkylhydroxyl- amine derived from hydrogenated tallow amine.

7. Thiosvnerqists, for example dilauryl thiodipropionate or distearyl thiodipropionate.

8. Peroxide scavengers, for example esters of ß-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyidithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (p- dodecylmercapto) propionate.

9. Polyamide stabilizers, for example copper salts in combination with iodides and/or phos- phorus compounds and salts of divalent manganese.

10. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitat, antimony pyrocatecholate or zinc pyrocatecholate.

11. Nucleating agents, for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals ; organic compounds, such as mono-or polycarboxylic acids and the salts thereof, e. g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate ; polymeric compounds, such as ionic copolymers (ionomers).

Especially preferred are 1, 3 : 2, 4-bis (3', 4'-dimethylbenzylidene) sorbitol, 1, 3 : 2, 4-di (paramethyl- dibenzylidene) sorbitol, and 1, 3 : 2, 4-di (benzylidene) sorbitol.

12. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, car- bon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.

13. Other additives, for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in U. S. 4, 325, 863 ; U. S. 4, 338, 244 ; U. S. 5, 175, 312 ; U. S. 5, 216, 052 ; U. S. 5, 252, 643 ; DE-A-4316611 ; DE-A-4316622 ; DE-A-4316876 ; EP-A-0589839 or EP-A-0591102 or 3- [4- (2-acetoxyethoxy)- phenyl]-5, 7-di-tert-butylbenzofuran-2-one, 5, 7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl]- benzofuran-2-one, 3, 3'-bis [5, 7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5, 7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3, 5-dimethylphenyl)-5, 7- <BR> <BR> <BR> di-tert-butylbenzofuran-2-one, 3- (3, 5-dimethyl-4-pivaloyloxyphenyl)-5, 7-di-tert-butylbenzofu- ran-2-one, 3- (3, 4-dimethylphenyl)-5, 7-di-tert-butylbenzofuran-2-one, 3- (2, 3-dimethylphenyl)- 5, 7-di-tert-butylbenzofuran-2-one.

The co-stabilizers are typically used in concentrations of 0. 01 to 10 %, based on the total weight of the material to be stabilized.

The novel compounds of the formula I can be used in particular together with phenolic anti- oxidants, light stabilizers and/or processing stabilizers.

Other preferred compositions comprise, in addition to compounds of the formula 1, a com- pound of the organic phosphite or phosphonite type.

The fillers and reinforcing agents (point 12 of the list), such as, for example, talc, calcium carbonate, mica or kaolin, are added to the polyolefins, for example, in concentrations of from 0. 01 to 40 %, based on the total weight of the polyolefins to be stabilized.

The fillers and reinforcing agents (point 12 of the list), such as, for example, metal hydr- oxides, especially aluminium hydroxide or magnesium hydroxide, are added to the polyole- fins, for example, in concentrations of from 0. 01 to 60 %, based on the total weight of the polyolefins to be stabilized.

Carbon black, as filler, is added to the polyolefins advantageously in concentrations of from 0. 01 to 5 %, based on the total weight of the polyolefins to be stabilized.

Glass fibres, as reinforcing agents, are added to the polyolefins advantageously in concen- trations of from 0. 01 to 20 %, based on the total weight of the polyolefins to be stabilized.

Also of interest as yet further additives in the compositions according to the invention are alkaline earth metal salts of higher fatty acids, such as, for example, calcium stearate ; cal- cium lactate and/or calcium stearoyl-2-lactylate.

As a conventional stabilizer combination for the processing of polymeric organic materials, such as, for example, polyolefins, into corresponding moulded articles, the combination of a phenolic antioxidant with a secondary antioxidant based on an organic phosphite or phos- phonite is recommended. Depending on the substrate and process, however, many poly- olefin processors are obliged to operate processes in the high-temperature range above approx. 280°C. The inclusion of a processing stabilizer of the formula I is particularly suitable for high-temperature applications, especially in the temperature range above 300°C. Tech- nical materials and moulded articles for instance based on HD polyethylene, such as, for example, pipes and their technical variants (fittings), can be manufactured with a higher out- put and fewer rejects. A further advantage of the compounds of the formula I is also that they can be used in a very small amount, which results in a reduction in the overall antioxi- dant concentration compared with conventional stabilizer mixtures. For instance the use of a low concentration of a compound of the formula I allows the overall stabilizer concentration to be reduced by approximately a third in, for example, polyolefins, which at the same time represents an economic advantage.

The compounds of the formula I and other optional additives are incorporated into the orga- nic polymeric material according to known methods, for example before or during shaping to moulded articles or alternatively by coating the organic polymeric material with a solution or dispersion of the compounds and subsequently evaporating the solvent. The compounds of the formual I can also be added to the materials to be stabilized in the form of a master batch which contains these compounds, typically in a concentration of, for example, from 2. 5 to 25 % by weight.

The compounds of the formula I may also be added before or during polymerization or be- fore crosslinking.

In this connection, particular attention is drawn to the surprising feature that the novel com- pounds of the formula I inhibit discoloration, especially so-called pinking in the manufacture of e. g. polyurethane foams.

The compounds of the formula 1, and where applicable further additives, may be incorpo- rated into the material to be stabilized in pure form or encapsulated in waxes, oils or poly- mers.

The compounds of the formula 1, and where applicable further additives, may also be sprayed onto the polymer to be stabilized. They are able to be used to dilute other additives (e. g. the above-mentioned conventional additives) or melts thereof, so that they can also be sprayed together with these additives onto the polymer to be stabilized. Application by spray- ing during the deactivation of the polymerization catalysts is especially advantageous, in which case spraying is conveniently effected with the vapour used for deactivation.

The materials stabilized in that manner may be used in an extremely wide variety of forms, e. g. in the form of films, fibres, tapes, moulding compounds or profiles, or as binders for surface-coatings, especially powder coatings, adhesives or cements.

The polyolefins stabilized in that manner may likewise be used in an extremely wide variety of forms, especially in the form of thick-layer polyolefin moulded articles that are in lasting contact with extracting media, such as, for example, pipes for liquids or gases, films, fibres, geomembranes, tapes, profiles or tanks.

The preferred thick-layer polyolefin moulded articles have a layer thickness of from 1 to 50 mm, especially from 1 to 30 mm, e. g. from 2 to 10 mm.

A preferred embodiment of this invention is therefore the use of compounds of the formula I for stabilizing organic materials against oxidative, thermal or light-induced degradation.

The invention also relates to a process for stabilizing an organic material against oxidative, thermal or light-induced degradation, which comprises incorporating therein or applying thereto at least one compound of the formula 1.

The invention relates also to compositions comprising a functional fluid, preferably from the series of lubricants, hydraulic fluids and metal-working fluids and also fuels for powering en- gines of the 4-stroke, Otto, 2-stroke, diesel, Wankel and orbital types, and at least one com- pound of the formula 1.

The compounds of the formula I may preferably be used in lubricants and fuels as multi- functional stabilizers, that is to say they combine in themselves antioxidative, friction-redu- cing, extreme-pressure-protection and wear-protection action and also anti-corrosion proper- ties.

Preferred lubricants and fuels and related products are engine oils, turbine oils, gear oils, hydraulic fluids, diesel or Otto fuels, metal-working fluids and lubricating greases.

Especially preferred lubricants are mineral oils, synthetic oils or mixtures thereof.

Products known per se are used as functional fluids from the series of lubricants, hydraulic fluids and metal-working fluids.

The lubricants and hydraulic fluids that come into consideration will be familiar to the person skilled in the art and are described in the relevant specialist literature, such as, for example, in Dieter Klamann,"Schmierstoffe und verwandte Produkte" [Lubricants and related pro- ducts] (Verlag Chemie, Weinheim, 1982), in Schewe-Kobek,"Das Schmiermittel-Taschen- buch" [The lubricant handbook] (Dr. Alfred Huthig-Verlag, Heidelberg, 1974) and in"Ull- manns Enzyklopädie der technischen Chemie" [Ullmann's Encyclopaedia of Industrial Che- mistry], Vol. 13, pages 85-94 (Verlag Chemie, Weinheim, 1977).

The lubricants are especially oils and greases, for example based on a mineral oil. Oils are preferred.

A further group of lubricants that may be used are vegetable or animal oils, greases, tallows and waxes or mixtures thereof with one another or mixtures with the mentioned mineral or synthetic oils.

Vegetable and animal oils, greases, tallows and waxes are, for example, palm-kernel oil, palm oil, olive oil, rapeseed oil, rape oil, linseed oil, groundnut oil, soybean oil, cottonseed oil, sunflower oil, pumpkin seed oil, coconut oil, maize oil, castor oil, tree nut oil and mixtures thereof, fish oils, tallows obtained from slaughtered animals, such as beef tallow, neatsfoot oil and bone oil, and modified, epoxidised and sulfoxidised forms thereof, for example epoxidised soybean oil.

The mineral oils are based especially on hydrocarbon compounds.

Examples of synthetic lubricants include lubricants based on aliphatic or aromatic carboxy esters, polymeric esters, polyalkylene oxides, phosphoric acid esters, poly-alpha-olefins or silicones, a diester of a divalent acid with a monohydric alcohol, such as, for example, dioctyl sebacate or dinonyl adipate, a triester of trimethylolpropane with a monovalent acid or with a mixture of such acids, such as, for example, trimethylolpropane tripelargonate, tri- methylolpropane tricaprylate or mixtures thereof, a tetraester of pentaerythritol with a mono- valent acid or with a mixture of such acids, such as, for example, pentaerythritol tetracapry- late, or a complex ester of monovalent and divalent acids with polyhydric alcohols, for example a complex ester of trimethylolpropane with caprylic and sebacic acid, or a mixture thereof. Apart from mineral oils there are especially suitable, for example, poly-alpha-olefins, ester-based lubricants, phosphates, glycols, polyglycols and polyalkylene glycols, and also mixtures thereof with water.

Metal-working fluids and hydraulic fluids may be prepared on the basis of the same sub- stances as those described above for the lubricants, such fluids frequently being emulsions of such substances in water or other liquids.

Lubricant and fuel compositions according to the invention are used, for example, in internal combustion engines, e. g. in motorised vehicles equipped with, for example, engines of the Otto, diesel, two-stroke, Wankel or orbital type.

The compounds of the formula I are readily soluble in lubricants and fuels, metal-working fluids and hydraulic fluids and are therefore especially suitable as additives for lubricants and fuels, metal-working fluids and hydraulic fluids.

As additives in lubricants, the compounds of the formula I are effective even in very small amounts. They are mixed in with the lubricants advantageously in an amount of from 0. 01 to 5 % by weight, preferably in an amount of from 0. 05 to 3 % by weight and very especially in an amount of from 0. 1 to 2 % by weight, in each case based on the lubricant.

The compounds of the formula I may be mixed in with the lubricants and fuels in a manner known per se. The compounds of the formula I are readily soluble, for example, in oils. It is also possible to prepare a so-called master batch, which may be diluted, as a function of use, with the appropriate lubricant or fuel to the concentrations suitable for use. In such cases concentrations above 1 % by weight are possible.

The lubricants and fuels, metal-working fluids and hydraulic fluids may additionally comprise other additives that are added in order to improve their basic properties still further ; such additives include : further antioxidants, metal passivators, rust inhibitors, viscosity index im- provers, pour-point depressants, dispersants, detergents, coefficient of friction reducers, fur- ther extreme-pressure additives and anti-wear additives. Such further additives are added advantageously in an amount of from 0. 01 to 5 % by weight.

A number of such compounds can be found, for example, in the above list"1. Antioxidants", especially points 1. 1 to 1. 19. In addition, further additives may be mentioned by way of example : Examples of further antioxidants : Aliphatic or aromatic phosphites, esters of thiodipropionic acid or thiodiacetic acid or salts of dithiocarbamic or dithiophosphoric acid, 2, 2, 12, 12-tetramethyl-5, 9-dihydroxy-3, 7, 11-tri- thiatridecane and 2, 2, 15, 15-tetramethyl-5, 12-dihydroxy-3, 7, 10, 14-tetrathiahexadecane.

Examples of metal deactivators. e. ci. for copper, are : a) Benzotriazoles and derivatives thereof, e. g. 2-mercaptobenzotriazole, 2, 5-dimercapto- benzotriazole, 4-or 5-alkylbenzotriazoles (e. g. tolutriazole) and derivatives thereof, 4, 5, 6, 7-tetrahydrobenzotriazole, 5, 5'-methylenebis-benzotriazole ; Mannich bases of benzotriazole or tolutriazole, such as 1- [di (2-ethylhexyl) aminomethyl] tolutriazole and 1- [di (2-ethylhexyl) aminomethyl] benzotriazole ; alkoxyalkylbenzotriazoles, such as 1- (no- nyloxymethyl) benzotriazole, 1- (1-butoxyethyl) benzotriazole and 1- (1-cyclohexyloxybutyl)- tolutriazole. b) 1, 2, 4-Triazoles and derivatives thereof, e. g. 3-alkyl- (or-aryl-) 1, 2, 4-triazoles, Mannich bases of 1, 2, 4-triazoles, such as 1-[di (2-ethylhexyl) aminomethyl]-1, 2, 4-triazole ; alkoxy- alkyl-1, 2, 4-triazoles, such as 1- (1-butoxyethyl)-1, 2, 4-triazole ; acylated 3-amino-1, 2, 4-tri- azoles. c) Imidazole derivatives, e. g. 4, 4'-methylenebis (2-undecyl-5-methyl) imidazole and bis [(N- methyl) imidazol-2-yl] carbinol-octyl ether. d) Sulfur-containing heterocyclic compounds, e. g. 2-mercaptobenzothiazole, 2, 5-dimer- capto-1, 3, 4-thiadiazole, 2, 5-dimercaptobenzothiadiazole and derivatives thereof ; 3, 5-bis- [di (2-ethylhexyl) aminomethyl]-1, 3, 4-thiadiazolin-2-one. e) Amino compounds, e. g. salicylidene-propylenediamine, salicylaminoguanidine and salts thereof.

Examples of rust inhibitors are : a) Organic acids, their esters, metal salts, amine salts and anhydrides, e. g. alkyl-and alkenyl-succinic acids and their partial esters with alcohols, diols or hydroxycarboxylic acids, partial amides of alkyl-and alkenyl-succinic acids, 4-nonylphenoxyacetic acid, alkoxy-and alkoxyethoxy-carboxylic acids, such as dodecyloxyacetic acid, dodecyloxy- (ethoxy) acetic acid and amine salts thereof, and also N-oleoyl-sarcosine, sorbitan mo- nooleate, lead naphthenate, alkenylsuccinic acid anhydrides, e. g. dodecenylsuccinic acid anhydride, 2-(2-carboxyethyl)-1-dodecyl-3-methylglycerol and salts thereof, espe- cially sodium and triethanolamine salts thereof. b) Nitrogen-containing compounds, e. g. : i. Primary, secondary or tertiary, aliphatic or cycloaliphatic amines and amine salts of organic and inorganic acids, e. g. oil-soluble alkylammonium carboxylates, and 1- [N, N- bis (2-hydroxyethyl) amino]-3- (4-nonylphenoxy) propan-2-ol. ii. Heterocyclic compounds, e. g. : substituted imidazolines and oxazolines, e. g. 2-hepta- decenyl-1- (2-hydroxyethyl)-imidazoline. c) Phosphorus-containing compounds, e. g. : Amine salts of phosphoric acid partial esters or phosphonic acid partial esters, zinc di- alkyldithiophosphates. d) Sulfur-containing compounds, e. g. : Barium dinonylnaphthalene sulfonates, calcium petroleum sulfonates, alkylthio-substi- tuted aliphatic carboxylic acids, esters of aliphatic 2-sulfocarboxylic acids and salts thereof. e) Glycerol derivatives, e. g. : Glycerol monooleate, 1- (alkylphenoxy)-3- (2-hydroxyethyl) glycerols, 1- (alkylphenoxy)-3- (2, 3-dihydroxypropyl) glycerols, 2-carboxyalkyl-1, 3-dialkylglycerols.

Examples of viscosity index improvers are : Polyacrylates, polymethacrylates, vinylpyrrolidone/methacrylate copolymers, polyvinylpyrrol- idones, polybutenes, olefin copolymers, styrene/acrylate copolymers, polyethers.

Examples of pour-point depressants are : Poly (meth) acrylates, ethylene/vinyl acetate copolymer, alkylpolystyrenes, fumarate copoly- mers, alkylated naphthalene derivatives.

Examples of dispersants/surfactants are : Polybutenylsuccinic acid amides or imides, polybutenylphosphonic acid derivatives, basic magnesium, calcium and barium sulfonates and phenolates.

Examples of extreme-pressure and anti-wear additives are : Sulfur-and/or phosphorus-and/or halogen-containing compounds, such as, for example, chlorinated paraffins, sulfurated olefins or vegetable oils (soybean/rape oil), alkyl-or aryl-di- or-tri-sulfides, zinc dial kyldithiophosphates, zinc dithiocarbamates such as zinc diamyldi- thiocarbamate, molybdenum dithioates such as molybdenum dithiocarbamates, triaryl phos- phates such as tritolyl phosphate, tricresyl phosphate, phenyl phosphate isopropyl ester, amine salts of mono-or di-alkylphosphoric acids such as the amine salts of mono-/di-hexyl phosphate, amine salts of alkylphosphonic acids such as the amine salt of methylphosphonic acid, triaryl phosphites such as tris [nonylphenyl] phosphite, dialkyl phosphites such as dioctyl phosphite, triaryl monothiophosphates such as triphenyl thionophosphate or tris [iso- nonylphenyl] thionophosphate or tert-butylated triphenyl thionophosphate, substituted trialkyl mono-or di-thiophosphates such as diisopropoxyphosphinothioyl) thio] propionate or butylene-1, 3-bis [(diisobutoxyphosphinothioyl) propionate, trithiophosphates such as trithio- phosphoric acid S, S, S-tris (isooctyl-2-acetates), amine salts of 3-hydroxy-1, 3-thiaphosphe- tane-3-oxide, benzotriazoles or derivatives thereof such as bis (2-ethylhexyl) aminomethyl- tolutriazole, dithiocarbamates such as methylene-bis-dibutyidithiocarbamate, derivatives of 2-mercaptobenzothiazole such as 1- [N, N-bis (2-ethylhexyl) aminomethyl]-2-mercapto-1H-1, 3- benzothiazole, derivatives of 2, 5-dimercapto-1, 3, 4-thiadiazole such as 2, 5-bis (tert-no- nyldithio)-1, 3, 4-thiadiazole.

Examples of coefficient of friction reducers are : Lard oil, oleic acid, tallow, rape oil, sulfurated fats, amines. Further examples are given in EP-A-0 565 487.

Examples of special additives for use in water/oil metal-working fluids and hydraulic fluids are : Emulsifiers : petroleum sulfonates, amines, such as polyoxyethylated fatty amines, non-ionic surface-active substances ; buffers : alkanolamines ; biocides : triazines, thiazolinones, tris-nitromethane, morpholine, sodium pyridenethol ; speed improvers : calcium and barium sulfonates ; Examples of fuel additives : Fuel additives are described in Kirk-Othmer, Encyclopedia of Chemical Technology, Vol 12, 1994 and in this instance are essentially petrol and diesel additives : Petrol : dyes, especially azo dyes ; Antioxidants : aminic, especially para-phenylenediamines, or phenolic, e. g. 2, 6-di-tert-butyl- phenol, as described above ; Metal deactivators : especially N, N'-disalicylidene-1, 2-propane, benzotriazole, EDTA ; Rust inhibitors : for example carboxylic acids, sulfonates, amines or amine salts ; Dispersants : e. g. esters, high-molecular-weight amines, Mannich bases, succinimides, borated succinimides ; Detergents : for example fatty acid amides, nonpolymeric amines, polybutene succinimides, polyether amines, low-molecular-weight amines, sulfonates, salicylic acid derivatives ; Demulsifiers : for example long-chain alcohols or phenols containing poly-ethylene or -butylen groups ; Antiknock agents : tetralkyl lead, manganese methylcyclopentadienyltricarbonyl ; Oxygen compounds : esters of vegetable oils, ethers, alcohols for improving burn behaviour ; Diesel : ignition improvers (cetane improvers), e. g. alkyl nitrates, ether nitrates, alkyl diglycol nitrates, organic peroxides ; Stabilizers for, especially, cracked diesel : amines and other N-containing compounds that act as radical traps.

Especially preferred further additives in lubricants are aminic antioxidants, especially mix- tures of mono-and di-alkylated tert-butyl-/tert-octyl-diphenylamines.

The present invention relates also to the use of the components of the formula I for stabil- zing organic materials, especially as additives in lubricants and fuels, hydraulic fluids or me- tal-working fluids, preferably in hydraulic oils and gear oils. The use according to the inven- tion includes protection of the metal components to be lubricated against mechanical attrition (wear protection) and corrosion protection activity and also antioxidation activity-with res- pect both to the lubricant and to the metal components.

The present invention accordingly relates also to a method for improving the properties, du- ring use, of organic materials, especially lubricants and fuels, metal-working fluids and hy- draulic fluids, wherein a compound of the formula I is added to those materials.

The photographic materials according to this invention comprise a support bearing at least one layer of a light-sensitive silver halide emulsion.

Examples of color photographic materials according to this invention are color negative films, color reversal films, color positive films, color photographic paper, color reversal photogra- phic paper, color-sensitive materials for the dye diffusion transfer process or the silver dye bleach process.

Of especial interest is a color photographic recording material comprising, on a base, at least one blue-sensitive silver halide emulsion layer containing at least one yellow dye providing compound, at least one green-sensitive silver halide emulsion layer containing at least one magenta dye providing compound, at least one red-sensitive silver halide emulsion layer containing at least one cyan dye providing compound, and customary (non light sensitive) top layer (s) and interlayers separating the light-sensitive layers.

The layers of the color photographic material can be arranged in various orders as is well known in the art.

The compounds of the formula I can be contained in any of the layers of the photographic material, i. e. in any of the light sensitive silver halide emulsion layers or in a non light sensi- tive layer. For use as a Dox scavenger, the compound of the formula I is preferably con- tained in one or more non light sensitive layers. In this case, the light sensitive layers may contain a lower concentration of a compound of the formula I or none.

The compounds of the formula I are preferably incorporated in an interlayer, especially a non-photosensitive interlayer, adjacent to the green-sensitive layer containing a magenta coupler. Preferred color photographic materials within this invention are those wherein the magenta coupler is of the pyrazolo-azole type, e. g. as disclosed in U. S. 5, 538, 840, column 49, line 51, until column 69, line 27, and publications cited therein ; this section of U. S.

5, 538, 840 is hereby incorporated by reference.

Also preferred is a color photographic material, wherein the silver halide emulsion contains at least 95 mol-% AgCI.

In general, the compounds of the formula I are contained in the photographic material in an amount from 10 to 1000 mg/m2, especially from 30 to 500 mg/m2.

The compounds of formula I can be milled with polymers (e. g. PVS, polyester, polyvinyl alco- hol etc.) and placed in a layer thus preventing their migration to adjacent layers. Also, com- pounds of formula I containing a suitable functional group (e. g. ester, hydroxy) can be reac- ted with a polymer, e. g. a polyvinyl alcohol or polyester, in order to attach them chemically.

This form will reduce their migrating tendency.

Typical bases for the photographic material include polymeric films and paper (including polymer-coated paper). Details regarding supports and other layers of color photographic recording materials can be found in Research Disclosure, Item 36544, September 1994.

Essential constituents of the photographic emulsion layers are binders, silver halide particles and color couplers. Details regarding the constituents of the light sensitive layers and other (non light sensitive) layers such as top layers and interlayers separating the silver halide emulsion layers can be found in Research Disclosure, Item 38957, September 1996.

The invention therefore also pertains to a color photographic material comprising a com- pound of the formula 1, and to the use of a compound of the formula I as an additive in a color photographic material.

The invention also partains to a process for preventing migration of the oxidized developer in a color photographic material from one color sensitive layer to another by incorporating a compound of the formula I into said material.

The compounds of the formula I of present invention are of special advantage when incor- porated into photographic materials containing magenta couplers of the pyrazolotriazole class.

Examples for especially suitable yellow, magenta and cyan couplers to be used in combi- nation with compounds of the present invention are as given in U. S. 5, 538, 840, column 33, line 3, until column 73, line 34, and publications cited therein. These passages are hereby incorporated by reference.

The compounds of the formula I which can be used in the context of this invention can be incorporated into the color photographic recording material, on their own or together with the color coupler and with or without further additives, by pre-dissolving them in high-boiling organic solvents. Preference is given to the use of solvents which boil at higher than 160°C.

Typical examples of these solvents are the esters of phthalic acid, phosphoric acid, citric acid, benzoic acid or of fatty acids, and also alkylamides and phenols.

Further details on the structure of the color photographic material of the invention, and the components or further additives which can be employed in the novel material, can be found, inter alia, in U. S. 5, 538, 840, column 27, line 25, to column 33, line 2 ; and further in U. S. 5, 538, 840 from column 74, line 18, to column 106, line 16 ; and in U. S. 5, 780, 625, co- lumn 12, line 6, until column 57, line 6, and the publications cited in these 2 references ; these passages of U. S. 5, 538, 840 and U. S. 5, 780, 625 are hereby incorporated by reference.

Other useful information, how compounds of the formula I can be used in photographic ma- terial, can be taken from EP-A-0 871 066, page 10, line 10, until page 11, line 32, especially the references cited therein.

The photographic layers in the material of this invention may also include UV absorbers, which screen out the UV light and therefore protect the dyes, the couplers or other compo- nents against photodegradation. Hydroquinone compounds according to this invention may be contained in those layers where UV absorbers are present. UV absorbers preferably to be used in the novel material or within the process of present in- vention include benzotriazoles, 2-hydroxybenzophenones, oxanilides, cyanoacrylates, salicy- lic esters, acrylonitrile derivatives, thiazolines and 2-hydroxyphenyltriazines.

GB-A-2, 319, 523 describes from page 49, line 21, until page 73, line 2, further details of the color photographic material, especially couplers (page 52, line 1, until page 56, line 22), UV absorbers (page 56, line 25, until page 68, line 1) and dark stabilizers (page 68, line 2, until page 73, line 2). Preferred UV absorbers of the 2-hydroxyphenyltriazine class are also des- cribed in detail, for example, in U. S. 5, 668, 200, column 1, line 30, until column 7, line 55, and as specific examples from column 26, line 31, until column 32, last line, and, together with some advantageous UV absorbers of the benzotriazole class, in U. S. 5, 300, 414, column 2 to column 10, line 54. These sections of U. S. 5, 668, 200 and U. S. 5, 300, 414 are hereby incorporated by reference.

The compounds of formula I may be used in combination with any known Dox scavengers such as hydrazines, hydrazides, hydroquinones of e. g. formula HQ-1 or HQ-2 ; 6-hydroxy- chromanes of e. g. formula A-3, or hydroxylamines of e. g. formula A-4 HQ-1 HQ-2 A-3 As silver halide emulsions it is possible to use customary silver chloride, silver bromide or sil- ver iodide emulsions or mixtures thereof, such as silver chlorobromide and silver chloroio- dide emulsions, in which the silver halides may have all known crystal forms. The use of sil- ver chloride emulsions is accorded particular importance in the material of this novel pro- cess. The preparation of such emulsions and their sensitization are described in Research Disclosure, Item 307105, November 1989.

The compounds of the formula I may preferably also be used as stabilizers for ethylenically unsaturated resins against premature polymerization or crosslinking of the resins during transport or storage.

Preferred ethylenically unsaturated resins are for example liquid or resin-like monomers, oli- gomers, co-oligomers, polymers of co-polymers or mixtures thereof, which possess at least one ethylenically unsaturated bond and which are photo-polymerisable or curable with UV light.

The following Examples illustrate the invention further. Parts or percentages relate to weight.

Example 1 : Preparation of 5, 7-di-tert-butyl-3- (4-trifluoromethyl-phenyl)-3H-benzofuran-2-one (compound (101), Table 1). a) Preparation of 2, 4-di-tert-butyl-6- [piperidin-1-yl- (4-trifluoromethyl-phenyl)-methyl]-phenol (compound (201), Table 2).

8. 29 g (97. 33 mmol) of piperidine are added, at room temperature, to a solution of 7. 74 g (44. 43 mmol) of 4-trifluoromethylbenzaldehyde in 50 ml of toluene. The slightly yellow- colored solution is boiled under reflux for 4 hours ; approximately 1 ml of water is separated off using a water separator, and a solution of 8. 73 g (42. 32 mmol) of 2, 4-di-tert-butylphenol in 15 ml of toluene is then added dropwise. The reaction mixture is boiled at reflux for further 17 hours and then cooled to room temperature ; the solvent is distilled off using a vacuum rotary evaporator. Crystallisation of the residue from iso-propanol/methanol (1 : 1) yields 15. 04 g (79 %) of compound (201) (Table 2), m. p. 150-152°C. Molecular weight C27H36F3NO (447. 59). Analysis, calculated : C 72. 45 ; H 8. 11 ; N 3. 13 %. Analysis, found : C 72. 63 ; H 8. 05 ; N 3. 05 %.'HNMR (300 MHz, Ceci3, ppm) : 1. 12 (s, 9H) ; 1. 39 (s, 9H) ; 1. 56 (m, 4H) ; 2. 28 (bm, 6H) ; 4. 37 (s, 1 H) ; 6. 65 (d, 1 H) ; 7. 08 (d, 1 H) ; 7. 47 (m, 4H).

Compounds (202), (203) and (204) (Table 2) are obtained in analogy to Example 1 a using 3- trifluoromethylbenzaldehyde [for (202)], 2-trifluoromethylbenzaldehyde [for (203)] and 3, 5-di- trifluoromethylbenzaldehyde [for (204)] instead of 4-trifluoromethylbenzaldehyde. b) Preparation of 5, 7-di-tert-butyl-3- (4-trifluoromethyl-phenyl)-3H-benzofuran-2-one (com- pound (101), Table 1).

A solution of 12. 53 g (28. 0 mmol) of compound (201), prepared according to Example 1a, in 150 ml of dry toluene is degassed using argon and then 33. 6 mg (0. 057 mmol) of dichloro- [1, 3-bis (diphenylphosphino) propane] palladium (II) and 4. 22 ml (112 mmol) of formic acid are added. The autoclave is flushed with carbon monoxide and sealed, and a carbon monoxide pressure of 6 bar is then applied. The reaction mixture is maintained at 140°C for 14 hours.

After cooling to room temperature, the reaction mixture is poured into water and extracted three times using ethyl acetate. The organic phases are combined, dried over sodium sulfate and concentrated using a vacuum rotary evaporator. Filtration of the residue on silica gel using ethyl acetate and crystallisation of the pure fractions from methanol yields 9. 46 g (87 %) of compound (101) (Table 1), m. p. 127-128°C. Molecular weight C23H25F302 (390. 45).

Analysis, calculated : C 70. 75 ; H 6. 45 %. Analysis, found : C 70. 96 ; H 6. 53 %.'HNMR (300 MHz, CDCI3, ppm) : 1. 23 (s, 9H) ; 1. 37 (s, 9H) ; 4. 83 (s, 1H) ; 6. 97 (m, 1H) ; 7. 31 (m, 3H) ; 7. 57 (d, 2H).

Compounds (102), (103) and (104) (Table 1) are obtained in analogy to Example 1b using compounds (202), (203) and (204) (Table 2) instead of compound (201).

Example 2 : Preparation of 5, 7-di-tert-butyl-3- (4-fluorophenyl)-3H-benzofuran-2-one (com- pound (105), Table 1). a) Preparation of 2, 4-di-tert-butyl-6- [ (4-fluorophenyl)-piperidin-1-yl-methyl]-phenol (com- pound (205), Table 2).

8. 29 g (97. 33 mmol) of piperidine are added, at room temperature, to a solution of 5. 52 g (44. 43 mmol) of 4-fluorobenzaldehyde in 50 ml of toluene. The slightly yellow-colored solu- tion is boiled under reflux for 16 hours ; approximately 1 ml of water is separated off using a water separator, and a solution of 8. 73 g (42. 32 mmol) of 2, 4-di-tert-butylphenol in 15 ml of toluene is then added dropwise. The reaction mixture is boiled at reflux for further 16 hours and then cooled to room temperature ; the solvent is distilled off using a vacuum rotary eva- porator. Crystallisation of the residue from iso-propanol/methanol (1 : 1) yields 15. 40 g (91 %) of compound (205) (Table 2), m. p. 135-136°C. Molecular weight C26H36FNO (397. 58). Ana- lysis, calculated : C 78. 55 ; H 9. 13 ; N 3. 52 %. Analysis, found : C 78. 48 ; H 9. 09 ; N 3. 50 %.

'HNMR (300 MHz, CDC13, ppm) : 1. 12 (s, 9H) ; 1. 37 (s, 9H) ; 1. 57 (m, 4H) ; 2. 28 (bm, 6H) ; 4. 35 (s, 1 H) ; 6. 63 (d, 1 H) ; 6. 91 (dt, 2H) ; 7. 08 (d, 1 H) ; 7. 32 (bm, 4H). b) Preparation of 5, 7-di-tert-butyl-3- (4-fluorophenyl)-3H-benzofuran-2-one (compound (105), Table 1).

A solution of 11. 13 g (28. 0 mmol) of compound (205), prepared according to Example 2a, in 150 ml of dry toluene is degassed using argon and then 33. 6 mg (0. 057 mmol) of dichloro- [1, 3-bis (diphenylphosphino) propane] palladium (ll) and 4. 22 mi (112 mmol) of formic acid are added. The autoclave is flushed with carbon monoxide and sealed, and a carbon monoxide pressure of 6 bar is then applied. The reaction mixture is maintained at 140°C for 14 hours.

After cooling to room temperature, the reaction mixture is poured into water and extracted three times using ethyl acetate. The organic phases are combined, dried over sodium sulfate and concentrated using a vacuum rotary evaporator. Filtration of the residue on silica gel using ethyl acetate and crystallisation of the pure fractions from methanol yields 8. 53 g (90 %) of compound (105) (Table 1), m. p. 146-147°C. Molecular weight C22H25FO2 (340. 44).

Analysis, calculated : C 77. 62 ; H 7. 40 %. Analysis, found : C 77. 66 ; H 7. 35 %.'HNMR (300 MHz, CDC13, ppm) : 1. 22 (s, 9H) ; 1. 36 (s, 9H) ; 4. 74 (s, 1H) ; 6. 99 (m, 3H) ; 7. 16 (m, 2H) ; 7. 26 (d, 1 H).

Example 3 : Preparation of 5, 7-di-tert-butyl-3- (4-cyanophenyl)-3H-benzofuran-2-one (com- pound (106), Table 1). a) Preparation of 2, 4-di-tert-butyl-6- [ (4-cyanophenyl)-piperidin-1-yl-methyl]-phenol (com- pound (206), Table 2).

8. 29 g (97. 33 mmol) of piperidine are added, at room temperature, to a solution of 5. 83 g (44. 43 mmol) of 4-cyanobenzaldehyde in 50 ml of toluene. The slightly yellow-colored solu- tion is boiled under reflux for 4 hours ; approximately 1 ml of water is separated off using a water separator, and a solution of 8. 73 g (42. 32 mmol) of 2, 4-di-tert-butylphenol in 15 ml of toluene is then added dropwise. The reaction mixture is boiled at reflux for further 6 hours and then cooled to room temperature ; the solvent is distilled off using a vacuum rotary eva- porator. Crystallisation of the residue from methanol yields 12. 95 g (75 %) of compound (206) (Table 2), m. p. 165-166°C. Molecular weight C27H36N20 (404. 60). Analysis, calculated : C 80. 15 ; H 8. 97 ; N 6. 92 %. Analysis, found : C 80. 01 ; H 9. 00 ; N 6. 78 %.'HNMR (300 MHz, CDC13, ppm) : 1. 12 (s, 9H) ; 1. 36 (s, 9H) ; 1. 57 (m, 4H) ; 2. 28 (bm, 6H) ; 4. 34 (s, 1H) ; 6. 63 (d, 1 H) ; 7. 09 (d, 1 H) ; 7. 51 (m, 4H).

Compounds (207) and (208) (Table 2) are obtained in analogy to Example 3a using 3-cyano- benzaldehyde [for (207)] and 3, 5-dicyanobenzaldehyde [for (208)] instead of 4-cyanobenzal- dehyde. b) Preparation of 5, 7-di-tert-butyl-3- (4-cyanophenyl)-3H-benzofuran-2-one (compound (106), Table 1).

A solution of 11. 33 g (28. 0 mmol) of compound (206), prepared according to Example 3a, in 150 ml of dry toluene is degassed using argon and then 33. 6 mg (0. 057 mmol) of dichloro- [1, 3-bis (diphenylphosphino) propane] palladium (II) and 4. 22 ml (112 mmol) of formic acid are added. The autoclave is flushed with carbon monoxide and sealed, and a carbon monoxide pressure of 6 bar is then applied. The reaction mixture is maintained at 140°C for 14 hours.

After cooling to room temperature, the reaction mixture is poured into water and extracted three times using ethyl acetate. The organic phases are combined, dried over sodium sulfate and concentrated using a vacuum rotary evaporator. Filtration of the residue on silica gel using ethyl acetate and crystallisation of the pure fractions from methanol yields 7. 72 g (79 %) of compound (106) (Table 1), m. p. 136-137°C. Molecular weight C23H25NO2 (347. 46).

Analysis, calculated : C 79. 51 ; H 7. 25 ; N 4. 03 %. Analysis, found : C 79. 36 ; H 6. 98 ; N 3. 82 %.

'HNMR (300 MHz, CDC13, ppm) : 1. 23 (s, 9H) ; 1. 36 (s, 9H) ; 4. 83 (s, 1H) ; 6. 95 (m, 1H) ; 7. 31 (m, 3H) ; 7. 61 (d, 2H).

Compounds (107) and (108) (Table 1) are obtained in analogy to Example 3b using com- pounds (207) and (208) (Table 2) instead of compound (206).

Example 4 : Preparation of 5, 7-di-tert-butyl-3- (4-methoxycarbonylphenyl)-3H-benzofuran-2- one (compound (109), Table 1). a) Preparation of 2, 4-di-tert-butyl-6- [ (4-methoxcarbonylphenyl)-piperidin-1-yl-methyl]-phenol (compound (209), Table 2).

18. 98 g (222. 94 mmol) of piperidine are added, at room temperature, to a solution of 16. 71 g (101. 78 mmol) of 4-methoxycarbonylbenzaldehyde in 100 ml of toluene. The slightly yellow- colored solution is boiled under reflux for 15 hours ; approximately 2 ml of water is separated off using a water separator, and a solution of 20. 0 g (96. 93 mmol) of 2, 4-di-tert-butylphenol in 30 ml of toluene is then added dropwise. The reaction mixture is boiled at reflux for 1 hour and then cooled to room temperature ; the solvent is distilled off using a vacuum rotary eva- porator. Crystallisation of the residue from iso-propanol yields 32. 12 g (75 %) of compound (209) (Table 2), m. p. 167-168°C. Molecular weight C2aH39NO3 (437. 63). Analysis, calculated : C 76. 85 ; H 8. 98 ; N 3. 20 %. Analysis, found : C 76. 68 ; H 8. 84 ; N 3. 01 %.'HNMR (300 MHz, CDC13, ppm) : 1. 11 (s, 9H) ; 1. 37 (s, 9H) ; 1. 56 (m, 4H) ; 2. 30 (bm, 6H) ; 3. 82 (s, 3H) ; 4. 40 (s, 1 H) 6. 64 (d, 1 H) ; 7. 08 (d, 1 H) ; 7. 45 (bd, 2H) ; 7. 90 (dd, 2H). b) Preparation of 5, 7-di-tert-butyl-3- (4-methoxycarbonylphenyl)-3H-benzofuran-2-one (com- pound (109), Table 1).

A solution of 10. 50 9 (24. 0 mmol) of compound (209), prepared according to Example 4a, in 120 ml of dry toluene is degassed using argon and then 28. 8 mg (0. 048 mmol) of dichloro- [1, 3-bis (diphenylphosphino) propane] palladium (II) and 3. 62 mi (96 mmol) of formic acid are added. The autoclave is flushed with carbon monoxide and sealed, and a carbon monoxide pressure of 6 bar is then applied. The reaction mixture is maintained at 140°C for 14 hours.

After cooling to room temperature, the reaction mixture is poured into water and extracted three times using ethyl acetate. The organic phases are combined, dried over sodium sulfate and concentrated using a vacuum rotary evaporator. Filtration of the residue on silica gel using ethyl acetate and crystallisation of the pure fractions from methanol yields 7. 41 g (81 %) of compound (109) (Table 1), m. p. 135-136°C. Molecular weight C24H2804 (380. 49).

Analysis, calculated : C 75. 76 ; H 7. 42 %. Analysis, found : C 75. 67 ; H 7. 28 %.'HNMR (300 MHz, CDCI3, ppm) : 1. 22 (s, 9H) ; 1. 37 (s, 9H) ; 3. 85 (s, 3H) ; 4. 74 (s, 1H) ; 6. 96 (m, 1H) ; 7. 26 (m, 3H) ; 7. 98 (d, 2H).

Example 5 : Preparation of 5, 7-di-tert-butyl-3- (4-n-octyloxycarbonylphenyl)-3H-benzofuran-2- one (compound (110), Table 1).

A suspension of 14. 0 g (36. 80 mmol) of compound (109), prepared according to Example 4b, 23. 26 ml (147. 2 mmol) of 1-octanol and 92 mg (0. 368 mmol) of dibutyltinoxide (Bu2SnO) is heated at 170° C for 2 hours, whereas an orange solution is formed. Methanol is continu- ously distilled off the reaction mixture. After cooling to room temperature, the crude reaction mixture is treated with a 50 ml of a 1 : 19 mixture of ethyl acetate/hexane 1 : 1 and filtered through a pad of silica. Removal of the solvent using a vacuum rotary evaporator yields 17. 53 g (99%) of compound (110) (Table 1), as a pale yellow oil.'HNMR (300 MHz, CDC13, ppm) : 0. 90 (t, 3H) ; 1. 35 (s, 9H) ; 1. 38 (bs, 10H) ; 1. 46 (s, 9H) ; 1. 78 (q, 2H) ; 4. 33 (t, 3H) ; 4. 92 (s, 1 H) ; 7. 05 (s, 1 H) ; 7. 35 (d, 2H) ; 7. 36 (s, 1 H) ; 8. 07 (d, 2H).

Compounds (111), (112), (113), (114), (115), (116) and (117) (Table 1) are obtained in ana- logy to Example 5 using 1-dodecanol, 1-octadecanol, 1-nonadecanol, 1-docosanol, 2-ethyl- hexanol, 1, 6-hexanediol and 1, 12-dodecanediol instead of 1-octanol. For the preparation of compounds (116) and (117) only half of an equivalent of 1, 6-hexanediol and 1, 12-dodecane- diol in respect to the compound (109) was used.

Table 1 : no. compound 0 H C 3. C \ cl3 caf3 CH3 I 0 CCH3 \ H CF \ 3 102 cl3 CH3 CHUG ut3 3 H CF H3CCCH O s \ 103 H3 H3C-C-CH3 I 0 C3 O C CF3 104 CH. YJ 1 ! J i CH, 0 H3CCCH CF3 104 CH3 105 H3e F H3C. CCH3 O H uH3 0 H3C-C-CH3 I Table 1 : (continuation) no. compound o H3c, CH3 0 H 106 cH3 CN H3C-C-CH3 C3 O H3C. CCHs O H CL 0 Hr 3 ? \H H3C-C-CH3 C3 O CL, Con 108 H3 +CN i 108 !. J ' H CCCH CN CHI 0 H3c/CHI 0 H 109 CHI cOCH3 8H3 H, 0 Cl, t ; H3 0 H3C. CCHs O H 110 cH3 H3C-IC-CH3 O I I H3C-i-CH3 O UN3 Table 1 : (continuation) no. compound o HsC. CCHa O H "frYY 111 c 0- (CH2) 1, CH3 I I H3c-c-CHI 0 CH3 0 C 112 cH3 / CO- (CHz) nCHa I I H3C-C-CH3 0 CH3 c HsC. CCH3 O H 0 u 113 CHI c. O- (CH2) 18CH3 ici CL, 1 Ut3 HsC. CCHa O H 114 cH3 [I'I H3C-aC-CH3 0 I I HC-C-CH 0 L ; N3 0 Cl 0 CH3 115 O-CHF-CH- (CH,) 3CH3 ici H3C-C-CH3 0 CH3 Table 1 : (continuation) no. compound o H3c,/CH3 0 H 'YrY 116 CH3 0- (CHI)-- C 2 3 11 C3 1 O HsC. CCHa O H i \ 117 cH3 ( o-cH2) 6 ici H3C-C-CH3 0 CH3 2 2 Table 2 : no. compound H, C/OH ! H 201 c A CF3 201 IN cl3 CF3 H3C-C-CH3 CH3 202 H, CH N C-C CF3 H3C-C-CH3 CH3 0 r'u N H, C/OH) n pF, , __ /, CL, CH, 204 HIC Cl3 i i H3C-C-CH3 CH3 . To i ( C-C chez F H, C-C-CH, I Table 2 : (continuation) no. compound C/'OH H ce I CHEZ H3C-C-CH3 I cl, 207 H3"CH N CN CH3 , H3C-C-CH3 I CL3 208 H3, CN C"C cl3 H3C-C-CH3 CN I CH3 5 209 CC CH3 11 CL, CH3 Example 6 : Prevention of migration of the oxidized developer in a color photographic mate- rial.

To evaluate compounds of this invention with respect to their ability as interlayer scavengers for oxidized developing agent, three layer photographic test elements are prepared by providing layers in the order indicated on a polyethylene-coated paper support : Test element 1 (reference sample) (1) A photosensitive layer containing : -260 mg. m (based on silver) of an unsensitized silver bromide emulsion.

-1875 mg. m-2 of gelatin.

-250 mg. m-2 of magenta-dye-forming coupler M-2 -250 mg. m-2 of tricresylphosphate.

-2-sulfonate-4, 8-diisobutyl-naphtalene, sodium salt surface active agent.

-7-methyl-5-hydroxy-1, 3, 8-triazaindolizine antifoggant.

(2) An interlayer containing : -1800 mg. m-2 of gelatin.

-300 mg. m-2 of tricresylphosphate.

-2-sulfonate-4, 8-diisobutyl-naphtalene, sodium salt surface active agent.

(3) A layer containing : -1800 mg. m-2 of gelatin.

-180 mg. m~2 of dibutylphthalate.

-2-sulfonate-4, 8-diisobutyl-naphtalene, sodium salt surface active agent.

-2-hydroxy-4, 6-dichloro-1, 3, 5-triazine, potassium salt hardener.

Test element 2 (control sample) (1) A photosensitive layer having the same composition as the photosensitive layer of test element 1.

(2) An interlayer having the same composition as the interlayer of test element 1.

(3) A layer containing : -1800 mg. m-2 of gelatin.

-272 mg. m~2 of cyan-dye-forming coupler C-2 -180 mg. m-2 of dibutylphthalate.

-2-sulfonate-4, 8-diisobutyl-naphtalene, sodium salt surface active agent.

-2-hydroxy-4, 6-dichloro-1, 3, 5-triazine, potassium salt hardener.

Test elements 3 and 4 (1) A photosensitive layer having the same composition as the photosensitive layer of test element 1.

(2) An interlayer containing : -1800 mg. m-2 of gelatin.

-20 mg. m-2 of oxidized developer scavenger as indicated in Table 3 below -300 mg. m-2 of tricresylphosphate.

-2-sulfonate-4, 8-diisobutyl-naphtalene, sodium salt surface active agent.

(3) A layer having the same composition as the top layer of test element 2.

The test elements are imagewise exposed through a step wedge with density increment 0. 15 and thereafter subjected to the AGFA P-94 developing process.

Upon processing of the test elements, some oxidized developer is prone to migrate from the layer in which it is formed, for example the undermost, magenta-dye-providing layer, to the topmost layer containing the cyan-dye-forming coupler, thereby producing unwanted cyan dye. The amount of cyan dye that is generated depends on the ability of the interlayer to pre- vent the diffusion of oxidized developer. The cyan density at the exposure amount giving a magenta density of 1. 5 is reported in Table 3. Any cyan density inferior to that observed for test element 2 indicates scavenging of the oxidized developer.

Table 3 : Test element interlayer scavenger Cyan density at a magenta density of 1. 5 1 (reference) 0. 239 2 (control) 0. 293 3 Compound (109) 0. 254 4 Compound (101) 0. 253 1 It is clear from the data in Table 3 that compounds within the scope of this invention are quite effective in preventing the oxidized developer from wandering and forming dye in the wrong layer.

Example 7 : Stabilization of multiple-extruded polypropylene.

1. 3 kg of polypropylene powder (Profax 6501), which has been prestabilized with 0. 025 % of Irganox 1076 (n-octadecyl 3- [3, 5-di-tert-butyl-4-hydroxyphenyl] propionate) (melt index 3. 2 g/10 min, measured at 230°C/2. 16 kg) are blended with 0. 05 % of Irganox@1010 (penta- erythritoltetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate]), 0. 05 % of calcium stea- rate, 0. 03 % of DHT 4A (Kyowa Chemical Industry Co., Ltd., [Mg4sAl2 (0H) 13CO3-3. 5 H2O]) and 0. 05 % of compound of Table 4. This blend is then extruded in an extruder having a cylinder diameter of 20 mm and a length of 400 mm at 100 rpm, the 3 heating zones being adjusted to the following temperatures : 260, 270, 280°C. The extrudate is cooled by drawing it through a water bath and is then granulated. This granulate is repeatedly extruded. After 3 extrusions, the melt index is measured (at 230°C/2. 16 kg). A substantial increase in the melt index denotes pronounced chain degradation, i. e. poor stabilization. The results are summa- rized in Table 4.

Table 4 : Compound of Melt index after 3 Table 1 extrusions 17. 5 101 4. 7 105 4. 7 106 4. 7 109 4. 8 110 4.7 Example 8 : Stabilization of polyethylene during processing.

100 parts of polyethylene powder (Lupolen 5260 Z) are blended with 0. 05 part of Irganox @1010 (pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate]) and 0. 05 part of a compound of Table 5 and the blend is kneaded in a Brabender plastograph at 220°C and 50 rpm. During this time the kneading resistance is recorded continuously as torque. In the course of the kneading time the polymer begins to crosslink after prolonged constancy, as can be determined by the rapid increase in torque. The time taken until a marked in- crease in torque is shown in Table 5 as a measure of the stabilizing action. The longer this time is the better the stabilizing action.

Table 5 : Compound of Time until increase Table 1 in torque (min) 9. 7 101 27. 5 105 27. 0 106 27. 5 109 27. 5 110 27.5 Example 9 : Stabilization of multiple-extruded polypropylene at high temperature.

1. 5 kg of polypropylene powder (Profax 6501), which has been prestabilized with 0. 008 % of Irganox1076 (n-octadecyl 3- [3, 5-di-tert-butyl-4-hydroxyphenyl] propionate) (melt index 3. 2 g/10 min, measured at 230°C/2. 16 kg) are blended with 0. 05 % of IrganoelOlO (penta- erythritoltetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate]), 0. 10 % of calcium stea- rate and 0. 015 to 0. 100 % of stabilizer or stabilizer mixture according to Table 6. This blend is then extruded in an extruder having a cylinder diameter of 20 mm and a length of 400 mm at 100 rpm, the 3 heating zones being adjusted to the following temperatures : 280, 320, 340°C. The extrudate is cooled by drawing it through a water bath and is then granulated.

This granulate is repeatedly extruded. After 5 extrusions, the melt index is measured (at 230°C/2. 16 kg). A substantial increase in the melt index denotes pronounced chain degra- dation, i. e. poor stabilization. The results are summarized in Table 6.

Table 6 : Melt index after 5 Stabilizers Concentration in extrusions % (by weight) 2800C 3200C 3400C Irgafos@1 68a) 0. 100 9. 7 43. 8 80. 1 Sandostab@P-EPQb) 0. 050 6. 3 23. 9 61. 5 Compound (101) 0. 015 8. 5 19. 6 22. 5 Irgafos#168a) 0.045 7. 2 24. 2 26. 5 Compound (101) 0. 005 SandostabP-EPQ 0. 045 5. 7 15. 9 24. 7 Compound (101) 0. 005 For footnotes a) and b) see the end of Table 25.

Example 10 : Preparation of polyether/polyurethane soft foams as well as the stabilization thereof.

Exactly 470 mg (0. 3 %, based on the polyol) of a stabilizer mixture of this invention is dis- solved in 157 g of an antioxidant-free polyether/polyol, Lupranol°2045 (trifunctional poly- ether/polyol having primary hydroxyl groups ; hydroxyl number 35 mg KOH/g, water content less than 0. 1 %, acid number less than 0. 1 mg KOH/g). 10. 24 g of a solution consisting of 1. 74 g Tecostab$ (polysilicone supplied by Goldschmidt, Germany], 0. 48 g diazabicyclooc- tane (amine catalyst) and 0. 8 g of water are added and the reaction mixture is stirred vigo- rously for 60 seconds at 100 rpm. 3. 2 g of a solution of 0. 32 g of tin octoate (catalyst) in 2. 9 g of the above polyol is added and the reaction mixture is again stirred vigorously for 60 se- conds at 100 rpm. With vigorous stirring, 98 g of an isocyanate (Lupranat@T80, supplied by BASF ; toluylene-2, 4- and toluylene-2, 6-diisocyanate mixture) are then added immediately and after 6 seconds the mixture is poured into a lined mould and the exothermic temperature is measured during foaming to a foam block. The foam blocks are cooled for 24 hours in a climatic chamber at 5°C and stored. 2 cm slices are sawed from the center of the blocks and round (cylindrical) test samples are cut therefrom using a boring tool. The samples are aged in a test tube in the presence of air at room temperature and 200°C for 30 minutes in a pre- heated alu-block thermostat (dynamic heat test). The yellowing of these test samples is de- termined as Yellowness Index (YI) according to ASTM D-1925-77. Low YI values denote little discoloration, high YI values severe discoloration of the samples. The results are summa- rized in Tables 7 and 8.

Table 7 : Example Concentration of stabilizers in YI YI % (by weight) room temp. 200°C 10a"--1. 0 70. 0 10bk) 0. 15 % Compound (101) 1 1 2. 0 0.15 % Irganox#5057c) -1.1 2.0 10ck) 0. 15 % Compound (102) 0.15 % Irganox#5057c) -0.9 1.8 10dk) 0. 15% Compound (104) 0.15 % Irganox#5057c) -1.3 2.0 Table 8 : Example Concentration of stabilizers inYI YI % (by weight) room temp. 200°C 10ei) 0. 5 69. 0 0. 10 Compound (101) 10fk) 0.10 % Irganox#5057c) -1. 1 2. 1 0. 10 % Irganoxe1135d) 0. 10 % Compound (102) 10gk) 0.10 % Irganox#5057c) -0. 9 1. 9 0. 10 % Irganox@1 1 35d) 0. 10 % Compound (104) 10hk) 0. 10 % Irganox@5057C)-1. 3 2. 0 0. 10 % IrganoxX1 1 35d) For footnotes c), d), i) and k) see the end of Table 25.

Example 11 : Stabilizing polypropylene fibers processed at 300°C.

2. 0 kg of polypropylene powder (B 10 FBs from Polychim S. A., France), which has a melt index of 12. 0 g/dmin measured in accordance with DIN 53735 at 230°C under 2. 16 kg, is homogenized with 0. 05 % of calcium stearate and with the stabilizers indicated in Tables 9 and 10 for 2 minutes in a high-speed mixer. This mixture is extruded at 60 revolutions per minute in an extruder having a barrel diameter of 20 mm and a length of 400 mm, the three heating zones being set at the following temperatures : 200, 220 and 220°C. The extrudate is passed through a water bath for cooling and then granulated. These granules are processed to give a multifilament fiber. This is done using a single-screw extruder with a melt pump and a 37-hole spinning head. The maximum processing temperature is 300°C.

A portion of the unstretched fiber thus obtained is pressed for 6 minutes at 230°C to form a sheet with a thickness of 2 mm. The melt index (MFI, melt flow index) of this sheet is mea- sured in accordance with DIN 53735 at 230°C and 2. 16 kg. A large increase in the melt in- dex denotes severe chain degradation and thus poor stabilization. The results are compiled in Table 9.

Another portion of the unstretched fiber thus obtained is treated with a lubricant (Limanol@P 25, Schill und Seilacher, Boblingen, Germany) and subjected to preliminary drawing. This preliminary drawing leads to a fiber strand having a linear density of 416 g/90 m. This means that a fiber strand 90 m in length has a weight of 416 g. In a further operation, this fiber strand is again drawn at 120°C by a factor of 3. 2 using a drawing apparatus. This leads to a fiber strand having a linear density of 130 g/90 m.

A portion of this fiber strand is used to produce a knitted tube. The yellowness index (Y) i) of this knitted tube is determined in accordance with ASTM D 1925-77. Low Yl, values denote little discoloration, high YI, values severe discoloration of the samples. The results are com- piled in Table 9. This knitted tube is exposed in the presence of from 4 to 6 ppm nitrogen dioxide (NO2) at 40°C and 87 % relative atmospheric humidity for 48 hours in accordance with AATCC 164. The yellowness index (Yts) of this exposed knitted tube is determined in accordance with ASTM D 1925-77. Low Y12 values denote little discoloration, high Y12 values severe discoloration of the samples. The results are compiled in Table 9.

Another portion of the fiber strand is used to carry out an oven ageing test at 100°C. In this test, a measurement is made, in days, of the time taken for the fiber strand to tear under the test conditions. The longer the period before tearing of the fiber strand, the better the stabi- lization. The results are compiled in Table 10.

Another portion of the unstretched fiber is pressed for 6 minutes at 230°C to form a thin film with a thickness of 0. 10 mm. This film is subjected to a Xenon test in accordance with DIN 53387. In this test, the film is exposed in a Xenon 1200 weathering apparatus until a carbonyl index of 0. 25 is observed in the wavelength range from 1760 to 1680 cm \ The larger the number, the better the stabilization. The results are compiled in Table 10.

Table 9 : Example Stabilizers Yl1 after Yl2 after MFI after spinning NO2 exposure spinning 11ai) 0. 3 1. 2 110. 0 11 k) 0. 100% Compound (106)"g. g'g 0. 050 % Tinuvin#622) 11ck) 0. 100 % Compound (106).. 0. 050 % Chimassorb#944f) 11dk) 0.100 % Compound(106) 0.6 4.2 31.8 0. 050 % Chimassorb#119g) 0. 075 % Compound (106) 11ek) 0. 050 % Tinuvin@622e) 0. 6 4. 6 32. 3 0. 075 % Irgafos#168a) 0. 075 % Compound (106) 11fk) 0. 050 % Chimassorb#944f) 1. 4 5. 9 33. 5 0. 075 % Irgafos@168a) 0. 075 % Compound (106) 0.050 % Chimassorb#944f) 1. 6 4. 6 31. 6 0. 075 % Irgafos@38h) 0. 075 % Compound (106) 11 hk) 0. 050 % Chimassorb#119g) 1. 5 4. 7 32. 5 0. 075 % Irgafos#168a) For footnotes a), e), f), g), h), i) and k) see the end of Table 25.

Table 10 : Example Stabilizers Oven ageing Xenon test (days) (hours) 11a') 1 195 k) 0. 100% Compound (106) 38 c 050 % Chimassorb#944f) 11dk) 0. 100 % Compound (106) 37 1580 0. 050 % Chimassorb1199 0.075 % Compound (106) 11fk) 0.050 % Chimassorb#944f) 39 1320 0. 075 % Irgafos#168a) 0. 075 % Compound (106) 11gk) 0.050 % Chimassorb#944f) 39 1325 0. 075 % Irgafos@38h) 0. 075 % Compound (106) 11 hk) 0. 050 % Chimassorb@1199) 38 1610 0. 075 % Irgafos#168a) For footnotes a), f), g), h), i) and k) see the end of Table 25.

Example 12 : Preparation of polyolefin hollow articles by the rotomolding process.

100 Parts of low density polyethylene, copolymerized with hexene (PE-LLD), type Quantum, 5 Petrothenes GA-635-661, having a melt flow index of 6. 5 g/10 min and a density of 0. 935 g/cm3, are mixed with 0. 170 part of Chimassorbe 944 [formula see footnote (b) after Table 10], 0. 050 part of zinc stearate and the stabilizers cited in Tables 11 and 12 at 232°C in a Superior/MPM Extruder, fitted with a 24 : 1 Maddock type UD screw, at 100 revolutions per minute. The polymer is then ground. The particle size of the polymer is from 150 to 500 lim.

Owing to the larger surface of the particles obtained by grinding, the heat can be absorbed faster, which goes hand in hand with a lower energy consumption.

The actual rotomolding process or rotational molding process, which permits the production of fairly large three-dimensional solids, is carried out in a Clamshell type rotomolder FSP M20. In this machine, an aluminium mold, which is mounted on an arm and into which the plastic sample is filled, is heated with a gas burner with circulation of the hot air over 5 mi- nutes to 316°C, or over 6 minutes to 329°C, and is then kept at this temperature for a spe- cific time (see Tables 11 and 12). Subsequently, the oven is opened and the mold is cooled first for 7 minutes with circulating air, then for 7 minutes by spraying with water and finally for another 2 minutes with circulating air. During the entire heating and cooling process, the mold, which is mounted on two axes at right angles to each other, is rotated, the speed of the main axis being kept at 6 revolutions per minute and the rotational ratio being 4. 5 : 1.

After cooling, the lid of the mold is opened and the resultant hollow article is taken out. The yellowness index (YI) of the exterior of the molded articles is determined according to ASTM D 1925-70. Low YI values denote little discoloration, high Y values strong discoloration of the samples. The less discoloration, the more effective the stabilizer. The results are sum- marized in Tables 11 and 12.

Table 11 : Rotomolding at 316°C Yellowness Index after Examples Stabilizer 8 minutes 10 minutes Example 12ai) 0. 05 % Irganox#1010l) 6. 2 17. 7 0.10 % Irgafos#168a) Example 12b k) 0. 02 % compound (107) 4. 2 5. 2 0.08 % Irgafos#168a) Table 12 : Rotomolding at 329°C Yellowness Index after Examples Stabilizer 6 minutes 8 minutes 0.05 % Irganox#1010l) Example 12ci) 3.9 16.5 0.10 % Irgafos#168a) 0.02 % compound (107) Example 12dk) 4.1 5.6 0.08 % Irgafos#168a) For footnotes a), i), k) and 1) see the end of Table 25.

Example 13 : Stabilisation of polyethylene which is in permanent contact with water.

0. 10 % by weight of calcium stearate and a stabilizer mixture comprising 0. 10 % by weight of irganox@1010 (pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate]), 0. 05 % by weight of Irgafoel 68 (tris (2, 4-di-tert-butylphenyl) phosphite) and 0. 05 % by weight of compound (104) (Table 1) is added dry to a polyethylene polymer (Hostalenes CRP 100 ; PE-HD) taken direct from a reactor and are incorporated therein in a Pappenmaier mixer (type 20) within 2 minutes.

In an extruder, of Schwabenthan, the stabilized polyethylene is homogenised and processed to granulate. For the extraction tests in water, 200 mm by 150 mm by 2 mm test plates are pressed from the granulate of the individual formulations using a table press. To ease the moulding of the test plates, the pressing process is carried out between two aluminium foils.

The stabilizer extraction tests are carried out with deionised water. Preliminary heating of the extraction vessels is carried out in a circulating air oven, of Heraeus (Hanau, Germany), at a maximum temperature deviation of 1. 5°C. Glass vessels are used for extraction tests below the boiling point of water, such as at 80°C. Owing to the risk of oversaturating the water with stabilizers, the amount of liquid used for the tests is fixed at c. 400 mi per c. 70 g of polymer and the water is replaced with fresh water at regular intervals, i. e. whenever a sample is taken.

The test plates are subjected to the above test conditions for 50 days at 80°C. Upon termination of the extraction test, the residual stabilizer content and the oxidation induction time of the test plates are determined.

The residual content of sterically hindered phenol, Irganox81010, is determined using an internal standard in an HPLC appliance of the Spectra Physics SP 8800 type, equipped with autosampler and UVNIS detector of the Spectra 200 type. The chromatography is carried out at room temperature using a Hyperchrome 125 x 4. 6 mm type column which is filled with Nucleosil C 185 Rm. The injection volume is 14 Rl at a flow rate of 1. 5ml/minute. UV detection takes place at 270 nm.

The oxidation induction time which is determined using a"DuPont-instrument 910 Differen- tial Scanning Calorimeter", of TA Instruments (Alzenau, Germany), and taking a 5 to 10 mg amount of sample, describes the time in minutes at constant thermal stress (1 90°C/O2) up to the start of the complete degradation of the polyethylene sample. The longer the oxidation induction time, the better stabilized the polyethylene and the more stable is the polyethylene against extracting water with which it is in permanent contact. The results show that the stability of polyolefins which are in permanent contact with extracting media is improved if they contain a compound of the formula I according to the instant invention as stabilizer.

Example 14 : Measuring the discoloration of powder coatings based on a carboxy-functional polyester and cured in electric and gas ovens.

To prepare the powder coating composition based on a carboxy-functional polyester, compo- nents 1 to 6 (formulation without additives) or components 1 to 7 (formulation containing the stabilizers) are employed in the sequence indicated (cf. Table 13).

Table 13 : Examples (amount in grams) Components 1a 1b to 1i 1. Cryicoaf 360a) 591 591 2. Araldits GT 7004b) 394 394 3. Octadecyltrimethylammonium bromideC) 3. 6 3. 6 4. Resiflowe PV 88d) 12 12 5. Benzoine) 3 3 6. Titanium dioxide type R-KB-5 500 500 7. Stabilizers (see Tables 14 and 15)-6 Total : 1503. 6 1509. 6 a) Crylcoats 360 from UCB S. A., Drogenbos, Belgium. b) Araldits GT 7004 (Ciba Specialty Chemicals Inc.) is a bisphenol A diglycidyl ether. c) Octadecyltrimethylammonium bromide from Fluka AG, Buchs, Switzerland. d) Resiflows PV 88 from Worlee Chemie GmbH, Lauenburg, Germany. e) Benzoin from Fluka AG. f) Titanium dioxide type R-KB-5 from Bayer AG, Leverkusen, Germany.

The components weighed out in this way are mixed using a planetary stirrer. The mixture is then extruded on a prism extruder at 300 revolutions/minute and at 100°C and is rolled out.

The powder coating composition is coarsely comminuted using a bench cutter and is ground in a Retsch ZM-1 ultracentrifugal mill with a 0. 75 mm annular-perforation screen at 15, 000 revolutions/minute. Finally, the powder is passed through a 30 Rm screen on a centrifugal screening machine.

The finished powder coating composition is sprayed electrostatically to a coat thickness of 70 tm onto aluminium panels using an ESB-Wagner corona cup gun at 60 kV. Some of the coated panels are cured at 180°C for 90 minutes in an electric oven. The remaining coated panels are cured at 180°C for 45 minutes in a gas oven with an N02 content of 20 ppm. The yellowness index (YI) of the samples is determined in accordance with ASTM D 1925-70.

Low YI values denote little discoloration, high YI values denote severe discoloration of the samples. The less the discoloration, the more effective the stabilizer. The results are sum- marized in Tables 14 and 15.

Table 14 : Curing for 90 minutes in an electric oven at 180°C Examples Stabilizers Yellowness index after 90 minutes (% rel. to components 1 to 5) (ASTM D 1925-70) Example 14a''--3. 1 Example 14bk) 0. 60% Compound (110) 2. 7 0.50% Irgafos#168a) Example 14ck) 2.7 0.10% Compund (110) 0. 5% Irgafos@1 68a) Example 14d 0. 15% HALS mixturem) 2. 7 0. 30% Compound (110) 0. 15% Irgafos") 168 a) Example 14ek) 0.15% Irganox#1010l) 0. 30% Compound (110) For footnotes a), i), k), m) and I) see the end of Table 25.

Table 15 : Curing for 45 minutes in a gas oven at 180°C Stabilizers Yellowness index after 90 minutes Examples (% rel. to components 1 to 5) (ASTM D 1925-70) Example 14fi) 4. 2 Example 14gk) 0. 60% Compound (110) 3. 4 Example 0. 50%) rgafos168.,. Example 0.10% Compound (110) @ 0.15% Irgafos#168a) Example 14ik) 0. 15% HALS mixturem 3. 2 0. 30% Compound (110) For footnotes a), i), k) and m) see the end of Table 25.

Example 15 : Stabilizing polypropylene in the case of multiple extrusion and at especially high temperatures.

1. 5 kg of polypropylene powder (Profax#6501), which has been initially stabilized with 0. 008% of Irganox#1076 (n-octadecyl 3- [3, 5-di-tert-butyl-4-hydroxyphenyl] propionate) (with a melt index of 3. 2 measured at 230°C and under 2. 16 kg), are mixed with 0. 10% of calcium stearate and 0. 015 to 0. 20% of the stabilizers listed in Table 16. This mixture is extruded in an extruder having a barrel diameter of 20 mm and a length of 400 mm at 100 revolutions per minute, the maximum extruder temperature being set at 280, 300, 320 and 340°C. For cooling, the extrudate is drawn through a water bath and then granulated. These granules are extruded repeatedly. After 5 extrusions, the melt index is measured (at 230°C under 2. 16 kg). A large increase in the melt index denotes severe chain breakdown and hence poor stabilization. The results are summarized in Table 16.

Table 16 : Example Stabilizers Amount Melt index (% by wt.) after 5 extrusions Irgafos#168a) 0. 10 Example 15ai) Irganox#1010l) 0. 10 18. 2 Chimassorb#944f) 0. 20 Compound (101) 0. 015 Example 15bk) Irgafos@168a) 0. 10 gaz ) rganox1010"0. 05 Chimassorb8944f) 0. 10 Compound (101) 0. 015 Example 15ck) Irgafos#168a) 0. 10 gag Irganox#1010l) 0.05 Chimassorb#119g) 0. 10 For footnotes a), f), g), i), k) and 1) see the end of Table 25.

Example 16 : Stabilization of polycarbonate.

1. 0 kg of a polycarbonate powder which has been dried for 8 hours at 120°C in a vacuum drying oven (Lexan°115, of General Electric) and 0. 1 to 0. 6 g (0. 01 to 0. 06 %) of the stabi- lizers listed in Table 17 are mixed for 2 minutes in a Henschel mixer. This mixture is then ex- truded in a Schwabenthan extruder at a maximum of 280°C. The polymer string is then gra- nulated. Using an injection moulding machine, plates having a layer thickness of 2 mm are then moulded from the granulate so obtained at a maximum of 300°C. These plates are then aged in a circulating air oven at 135°C for 2000 hours. The yellowness index (YI) of these plates is then determined according to ASTM D 1925-70 and the transmission is determined in percent at 450 nm. Low YI values denote little discoloration, high YI values high discolo- ration of the patterns. The less discoloration, the more effective the stabilizer. The higher the transmission values, the more effective the stabilizer. The results are compiled in Tables 17 and 18.

Table 17 : Yellowness index Yellowness index Example Stabilizers after 2000 hours at prior to oven-ageing 135°C 135°C 16ai) 4. 2 25. 0 16bi) 0.05 % Irgafos#168a) 3. 4 23. 5 1 6ck) 0. 01 % Compound (101) 3. 4 16. 4 16d'"0. 01% Compound (112) 3. 5 14. 3 16ek) 0.05 % Irgafos#168a) 3.2 15. 2 0.01 % compound (101) 16fk) 0.05 % Irgafos#168a) 3.1 14.3 0.01 % compound (112) Table 18 : Transmission in % Transmission in % Example to oven-aging after 2000 hours at 135C 16ai) 84.7 76. 4 16bi) 0.05% Irgafos#168a) 84. 7 77. 8 16Ck) 0. 01 % Compound (101) 85. 8 81. 3 16dk) 0.01 % Compound (112) 85. 9 81.8 0.05 % Irgafos#168a) 16ek) 0. 01 % Compound (101) 16fk) 0. 05 % Irgafos#168a) 0. 01 % compound (112) For footnotes a), i) and k) see the end of Table 25.

Example 17 : Stabilization of polycarbonate. 1. 0 kg of a polycarbonate powder which has been dried for 8 hours at 120°C in a vacuum drying oven (Lexan"145, of General Electric) is charged with the stabilizers listed in Table 19 and is mixed for 2 minutes in a Henschel mixer. This mixture is then extruded in a Schwa- benthan extruder at a maximum of 280°C. The polymer string is then granulated. Using an injection moulding machine, plates having a layer thickness of 2 mm are then moulded from the granulate so obtained at a maximum of 300°C. These plates are then aged in a circu- lating air oven at 135°C, the time in hours until the yellowness index (YI) reaches a value of 20 according to ASTM D 1925-70 being measured. The longer the time, the more effective the stabilizer. The results are compiled in Table 19.

Table 19 : Example Stabilizers Time in hours at 135°C to YI = 20 17a') 1560 17bi) 0. 05 % IrgafosX168a) 2000 0. 006 % Compound (106) 17ck) 0. 022 % IrgafosX168a) 2350 0. 012 % Irganox#1076n) 0. 009 % Compound (106) 17dk) 0. 034 % Irgafos168a) 2350 0. 017 % Irganox#1076n) For footnotes a), i), k) and n) see the end of Table 25.

Example 18 : Stabilisation of polybutylene terephthalate (PBT).

1. 0 kg of a polybutylene terephthalate powder which has been dried for 10 hours at 100°C in a vacuum drying oven (Crastin@S600, of Ciba Specialty Chemicals Inc.) is charged with the stabilizers listed in Table 20 and is mixed for 2 minutes in a Henschel mixer. This mixture is then extruded in a twin-screw extruder (type Berstorff) at a maximum of 250°C and is then granulated. In an injection moulding apparatus, the granulate so obtained is moulded at a maximum of 260°C to little rods 4 x 6 mm thick and 50 mm long. These little rods are then aged in a circulating air oven at 160°C. After 360 hours the impact strength of the rods is measured in KJ/m2. The higher the values, the better the stabilization. The results are com- piled in Table 20.

Table 20 : Impact strength in the oven-ageing test at 160°C Impact strength in KJ/m2 Example Stabilizers after 0 h after 360 h 18ai) 130 26 18bi) 0. 05 % Irganoxs245°) 132 111 18c"0. 10%trganox245°' 135 114 i) 0.05% Irganox#245o) 0.05 % Irgafos#168a) 134 110 0. 05 % Irganox@245°) 18ek) 0. 05 % Irgafos@168a) 133 130 0. 02 % compound (109) d) For footnotes a), i), k) and o) see the end of Table 25.

Example 19 : Stabilization of polycarbonate.

1. 0 kg of a polycarbonate powder which has been dried for 8 hours at 120°C in a vacuum drying oven (Lexan#145, of General Electric) is charged with the stabilizers listed in Table 21 and is mixed for 2 minutes in a Henschel mixer. This mixture is then extruded in a Schwab- enthan extruder at a maximum of 280°C. The polymer string is then granulated. Using an injection moulding machine, plates having a layer thickness of 2 mm are then moulded from the granulate so obtained at a maximum of 300°C. These plates are then irradiated in a Weather-O-Meter (WOM Cl 65) for 2500 hours at a black standard temperature of 63°C, at a dry/wet cycle of 102/18 minutes and at an intensity of 0. 35 W/m2 at 340 nm. The yellowness index (YI) of these plates is then determined according to ASTM D 1925-70. Low YI values denote little discoloration, high YI values high discoloration of the plates. The less discolo- ration, the more effective the stabilizer or the stabilizer mixture. The results are compiled in Table 21.

Table 21 : Yellowness index Example Stabilizers after 2500 h exposure to light 30. 30. 2 19bi) 0.30 % tinuvin#234p) 17.8 19C ;) 0. 30 % Tinuvin@360q) 16. 6 19di) 0. 30 % Tinuvin@1577r) 11. 2 0. 30 % Tinuvin#234p) 0. 02 % Compound (102) 16. 5 19fk) 0. 30 % Tinuvin@360q) 0. 02 % Compound (102) 15. 0 19 0. 30 % Tinuvin#1477r) 9 0. 02 % Compound (102) 9.5 0. 30 % Tinuvin@234P) 19hk) 0.05 % Irgafos#168a) 13. 4 0. 02 % Compound (102) 0. 30 % Tinuvin#360q) 19ik) 0. 05 % Irgafos#168a) 12. 0 0. 02 % Compound (102) 0. 30 % Tinuvin#1577r) 19jk) 0.05 % Irgafos#168a) 9. 2 0. 02 % Compound (101) For footnotes a), i), k), p), q) and r) see the end of Table 25.

Example 20 : Stabilization of polycarbonate.

1. 0 kg of a polycarbonate powder which has been dried for 8 hours at 120°C in a vacuum drying oven (Lexan@145, of General Electric) is charged with the stabilizers listed in Table 22 and is then mixed for 2 minutes in a Henschel mixer. This mixture is then extruded in a Schwabenthan extruder at a maximum of 280°C. The polymer string is then granulated. The granulate so obtained is packed into 1 cm thick polystyrene boxes and the yellowness index (YI) is determined according to ASTM D 1925-70. Low YI values denote little discoloration, high Y values high discoloration of the samples. The less discoloration, the more effective the stabilizer or the stabilizer mixture. The results are compiled in Table 22.

Table 22 : Example Stabilizers Yellowness index 6a') 10. 6bi) 0. 05 % GSY$ P101s) 5. 1 k) 0. 04 % GSYe P101s) 1 0 0. 02 % Compound (104) For footnotes i), k) and s) see the end of Table 25.

Example 21 : Stabilization of polyesters.

2. 5 kg of a polyester which has been dried for 12 hours at 120°C in a vacuum drying oven (PolyclearX T86, of Hoechst) is charged with the stabilizers listed in Table 23 and is mixed for 2 hours in a Henschel mixer. This mixture is then extruded in a Schwabenthan extruder at a maximum of 275°C. The polymer string is then granulated. The granulate so obtained is dried for another 12 hours in a vacuum drying oven. In a double determination, 500 mg of the granulate is heated over 10 minutes to 290°C and is stored for 1 hour under pure oxygen in a rancimate at 290°C. The resulting gaseous separation products are continuously led into an aqueous collecting solution and the conductivity (, uS) of this solution is continuously mea- sured. Low conductivity values signify that few separation products are formed, high conduc- tivity values signify that very many separation products are formed. The lower the conducti- vity values, the more effective the stabilizer. The results are compiled in Table 23.

Table 23 : Example Stabilizers Conductivity (µS) 21 a' 47 21bk) 0. 20 % Compound (107) 34 For footnotes i) and k) see the end of Table 25.

Example 22 : Stabilization of light-colored SBR-vulcanisate (ozone atmosphere for 48 hours).

100 parts by weight of Cariflex@S-1502 (styrene/butadiene rubber, Shell) are processed at 60°C, in a mixing mill, with 30. 0 parts by weight of Kronos@CL 220 [titanium dioxide (pig- ment), Kronos Titan GmbH], 30. 0 parts by weight of Aktisil@MM [kaolin (filler), Hoffmann Mineral, Neuburg/Donau], 5. 0 parts by weight of NaftolenSN 401 [plasticizer, Metallgesell- schafts, 10. 0 parts by weight of zinc oxide [vulcanization activator], 2. 0 parts by weight of stearic acid [vulcanization activator], 2. 0 parts by weight of sulfur [vulcanizing agent], 1. 0 part by weight of Vulkacit@MOZ [vulcanisation accelerator, Bayer], 0. 25 part by weight of Vulka- citSThiuram [vulcanization accelerator, Bayer] and 1. 0 part by weight of the stabilizer to be tested according to Table 24, to form a homogeneous mixture, the vulcanization system (sul- fur, VulkacitSMOZ and Vulkacit@Thiuram) not being added until the end of the mixing pro- cess. The mixture is vulcanized in electrical vulcanization presses at 150°C until T95 is reached in the rheometer curves to form elastomer plates 2 mm thick, 21 cm long and 8. 0 cm wide.

Some of the elastomer plates so obtained are tested for the action of ozone according to the ASTM standard D 3395-86 while subject to dynamic elongation. In this test, the plates are first stored for 30 days in a standard atmosphere [23/50 SN-ISO 291]. Test specimens mea- suring 20 cm by 1 cm are then punched out and exposed to an ozone atmosphere for 48 hours (ozone content : 50 pphm ; temperature : 40°C ; humidity : 50 % rel. ; elongation : 0 to 25 % ; elongation rate : 0. 5 Hz ; number of load cycles : approximately 173 000). The test plates are then assessed for crack formation according to ASTM D 3395-86. Grade 0 de- notes no cracks ; grade 1 denotes narrow flat cracks ; grade 2 denotes moderately broad, moderately deep cracks, clearly visible ; grade 3 denotes broad and deep cracks. The lower the grade number, the better the stabilization of the elastomer plates. The results are com- piled in Table 24.

The remaining elastomer plates are stored for 3 weeks at room temperature in a standard laboratory atmosphere in diffuse daylight. The AL-color of those plates is then determined according to DIN 6167, which corresponds to a scale of from 0 to 100. No discoloration is indicated by a value of 100. The results are compiled in Table 24.

Table 24 : Crack formation AL-color Examples Stabilizer according to according to ASTM D 3395-86 DIN 6167 Example ssai) grade 1-2 94 Example 22b') 1. 0 phrU) Vulkanox@4010') grade 0 70 Example 22ck) 1. 0 phrU) Compound (108) grade 0-1 96 For footnotes i), k), t and u) see the end of Table 25.

Example 23 : Stabilisation of light-colored SBR-vulcanisate (ozone atmosphere for 96 hours).

100 parts by weight of Cariflex@S-1502 (styrene/butadiene rubber, Shell) are processed at 60°C, in a mixing mill, with 30. 0 parts by weight of Kronos@CL 220 [titanium dioxide (pig- ment), Kronos Titan GmbH], 30. 0 parts by weight of AktisilSMM [kaolin (filler), Hoffmann Mineral, Neuburg/Donau], 5. 0 parts by weight of NaftolenSN 401 [plasticiser, Metallgesell- schaft], 10. 0 parts by weight of zinc oxide [vulcanization activator], 2. 0 parts by weight of stearic acid [vulcanization activator], 2. 0 parts by weight of sulfur [vulcanizing agent], 1. 0 part by weight of Vulkacit@MOZ [vulcanization accelerator, Bayer], 0. 25 part by weight of Vulka- citathiuram [vulcanization accelerator, Bayer] and 1. 0 part by weight of the stabilizer to be tested according to Table 25, to form a homogeneous mixture, the vulcanization system (sulfur, Vulkacit@MOZ and Vulkacit@Thiuram) not being added until the end of the mixing process. The mixture is vulcanized in electrical vulcanization presses at 150°C until T95 is reached in the rheometer curves to form elastomer plates 2 mm thick, 21 cm long and 8. 0 cm wide.

Some of the elastomer plates so obtained are tested for the action of ozone according to the ASTM standard D 3395-86 while subject to dynamic elongation. In this test the plates are first stored for 30 days in a standard atmosphere [23/50 SN-ISO 291]. Test specimens mea- suring 20 cm by 1 cm are then punched out and exposed to an ozone atmosphere for 96 hours (ozone content : 50 pphm ; temperature : 40°C ; humidity : 50 % rel. ; elongation : 0 to 25 % ; elongation rate : 0. 5 Hz ; number of load cycles : approximately 173 000). The test plates are then assessed for crack formation according to ASTM D 3395-86. Grade 0 de- notes no cracks ; grade 1 denotes narrow flat cracks ; grade 2 denotes moderately broad, moderately deep cracks, clearly visible ; grade 3 denotes broad and deep cracks. The lower the grade number, the better the stabilization of the elastomer plates. The results are com- piled in Table 25.

The remaining elastomer plates are stored for 3 weeks at room temperature in a standard laboratory atmosphere in diffuse daylight. The AL-color of those plates is then determined according to DIN 6167, which corresponds to a scale of from 0 to 100. No discoloration is indicated by a value of 100. The results are compiled in Table 25.

Table 25 : Examples Stabilizer Crack formation AL-color according to according to ASTM D 3395-86 DIN 6167 Example 23a') grade 2 97 Example 23b') 2. 0 phru) Vulkanox#4010t) grade 0 56 Example 23ck) 2. 0 phrU) compound 101 grade 1 95 Example 23dk) 2. 0 phrU) compound 106 grade 1 95 Example 23ek) 2. 0 phrU) compound 108 grade 1 95 a) Irgafos@168 (Ciba Specialty Chemicals Inc.) is tris (2, 4-di-tert-butylphenyl) phosphite. b) Sandostab#P-EPQ (Clariant) is tetrakis (2, 4-di-tert-butylphenyl)-4, 4'-biphenylene diphos- phonite. c) Irganox@5057 (Ciba Specialty Chemicals Inc.) is a secondary amine antioxidant and is a technical mixture, obtained by reaction of diphenylamine with diisobutylene, comprising a') 3 % of diphenylamine ; b') 14 % of 4-tert-butyidiphenylamine ; c') 30 % of compounds of the group i) 4-tert-octyldiphenylamine, ii) 4, 4'-di-tert-butyldiphenylamine, iii) 2, 4, 4'-tris-tert-butyidiphenylamine ; d') 29 % of the compounds of the group i) 4-tert-butyl-4'-tert-octyldiphenylamine, ii) o, o'-, m, m'- or p, p'-di-tert-octyidiphenylamine, iii) 2, 4-di-tert-butyl-4'-tert-octyldiphenylamine ; e') 24 % of the compounds of the group i) 4, 4'-di-tert-octyldiphenylamine and ii) 2, 4-di-tert-octyl-4'-tert-butyidiphenylamine. d) Irganox@1135 (Ciba Specialty Chemicals Inc.) is a phenolic antioxidant of the formula A-1. e) Tinuvin@622 (Ciba Specialty Chemicals Inc.) is a compound of the formula H1 in which the average molecular weight is about 3000. f) Chimassorb"944 (Ciba Specialty Chemicals Inc.) denotes linear or cyclic condensation products prepared from N, N'-bis (2, 2, 6, 6-tetramethyl-4-piperidyl) hexamethylendiamine and 4-tert-octylamino-2, 6-dichloro-1, 3, 5-triazine and is a compound of the formula H2 in which the average molecular weight is about 2500.

(H2) g) Chimassorb@119 (Ciba Specialty Chemicals Inc.) denotes condensation products pre- pared from 2-chloro-4, 6-di (4-n-butylamino-1, 2, 2, 6, 6-pentamethylpiperidyl)-1, 3, 5-triazine and 1, 2-bis (3-aminopropylamino) ethane and is a compound of the formula H3 h) Irgafoss38 (Ciba Specialty Chemicals Inc.) is a compound of the formula P-1.

(P-1) i) Comparison Example. k) Example of this invention.

I) Irganox@1010 (Ciba Specialty Chemicals Inc.) denotes the pentaerythritol ester of 3- (3, 5- di-tert-butyl-4-hydroxyphenyl) propionic acid. m) HALS mixture is a 1 : 1 mixture of TinuvinS622 [Ciba Specialty Chemicals Inc. ; see foot- note e)] and Chimassorb@119 (Ciba Specialty Chemicals Inc. ; see footnote g)]. n) Irganox@1076 (Ciba Specialty Chemicals Inc.) denotes a compound of formula A-2.

(A-2) o) Irganox#245 (Ciba Specialty Chemicals Inc.) denotes a compound of formula A-3. p) Tinuvin234 (Ciba Specialty Chemicals Inc.) denotes a compound of formula UV-1. q) Tinuvin@360 (Ciba Specialty Chemicals Inc.) denotes a compound of formula UV-2.

(UV-2) r) Tinuvin#1577 (Ciba Specialty Chemicals Inc.) denotes a compound of formula UV-3.

(UV-3) s) GSYX P101 (Yoshitomi) denotes a compound of formula P-2. t) VulkanoxS4010 (Bayer) denotes 4-isopropylamino-diphenylamine of formula A. u) phr denotes"parts per hundred of rubber".