NL1008373C2 - Stabilizer mixture for organic materials. - Google Patents

Description

Stabilizer mixture for organic materials

The present invention relates to compositions comprising an organic material subject to oxidative, thermal or light-induced degradation, and as stabilizers at least one compound of the benzofuran-2-on type, at least one compound of the phosphite - or phosphonite type, comprising at least one phenolic antioxidant type compound and at least one sterically hindered amine type compound and its use for stabilizing organic materials against oxidative, thermal or light-induced degradation.

The use of benzofuran-2-on-type compounds as stabilizers for organic polymers is known, for example, from U.S. Pat. Nos. 325863, * 43882 * 4 * 4, 5175312, 52526 * 43, 15 5216052, 5369159. , 5356966, 5367ΟΟ8, 5 * 428162, 5 * 428177 or 5516920.

Organic phosphites, phosphonites and phosphoramides are known in the art as cost stabilizers, secondary antioxidants and processing stabilizers for polyolefins, among others. Examples of such known phosphite stabilizers can be found in R. Gachter / H. Müller (eds.), Plastics Additives Handbook, third edition, page * 47, Hanser, Munich 1990.

US Pat. No. 4,360,617 discloses that stabilizer mixtures comprising symmetrical triaryl phosphites and certain phenolic antioxidants are particularly suitable for protecting certain organic materials, such as polyurethane, polyacrylonitrile, polyamide-12, or polystyrene, against oxidative, thermal, or light-induced degradation .

Sterically hindered amines, including especially compounds containing 2,2,6,6-tetramethylpiperidyl groups, are known as hindered amine light stabilizers (HALS).

The known stabilizers do not meet the high requirements that a stabilizer must meet in every respect, in particular with regard to shelf life, water absorption, susceptibility to hydrolysis, in-process stabilization, coloring properties, volatility, migration behavior, compatibility and improvement of the protection from light. As a result, there remains a need for active stabilizers for organic materials that are sensitive to oxidative, thermal and / or light-induced degradation.

It has now been found that a stabilizer mixture containing at least one compound of the benzofuran-2-one type, at least one compound of the organic phosphite or phosphonite type, at least one compound of the phenolic antioxidant type and at least one compound of the type of the sterically hindered amines is particularly suitable as a stabilizer for organic materials sensitive to oxidative, thermal or light-induced degradation.

The present invention therefore provides compositions comprising a) an organic material that is subject to oxidative, thermal or light-induced degradation, b) at least one compound of the benzofuran-2-on type, c) at least one compound from the group of the organic phosphites or phosphonites, d) at least one compound from the group of the phenolic antioxidants and e) at least one compound from the group of the sterically hindered amines.

Compositions of interest include those which comprise as component (b) a compound of the formula I t "

O

25 R2 2Ύ> '- e> T iï Ri (o R * -In 30 where, if η is 1,

Rt unsubstituted or naphthyl substituted by C 1 -C 4 alkyl, O 1 -O 4 alkoxy, C 1 -C 4, alkylthio, hydroxyl, halogen, amino, Cx-C 1 alkylamino, phenylamino or di (C 1 -C 15 alkyl) amino , phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo [b] thienyl, naphto [2,3-b] thienyl , thiantrenyl, dibenzofuryl, chromenyl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidin-1008373 3 nyl, pyridazinyl, indolizinyl, isoindolyl, quinolinyl, quinolazinyl, quinolizinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, bi-phenyl, terphenyl, fluorenyl or phenoxazinyl formula II, or R9 is R8

Yj and if n is 2,

R 1 is unsubstituted or C 1 -C 4 alkyl or hydroxyl-substituted phenylene or naphthylene; or -R12_X-R13_, R 2, R 1 -R 1 and Rp independently of one another is hydrogen, chlorine, hydroxyl, 20 C, -C 2; alkyl, C7-C9 phenylalkyl, unsubstituted or C 1 -C * alkyl substituted phenyl; unsubstituted or C 1 -C 8 alkyl substituted C 5 -C 8 cycloalkyl; Cj-Cl8 alkoxy, Cj-Cjg alkylthio, Cj-C *, alkyl-amino, di {Cj-Ci, alkyl) amino, Cj-C25 alkanoyloxy, Cj-C25 alkanoylamino, CrC25 alkenoyloxy, C3-C25 alkanoyloxy oxygen,

25 I

sulfur or N-R1 ^; C6-C9 cycloalkylcarbonyloxy, benzoyloxy or with Cj-C12

alkyl substituted benzoyloxy; or else the groups R2 and R3 or the groups R3 and R /, or the groups RA and R &, together with the carbon atoms to which they are attached, form a benzo ring, R ^ additionally - (CH2) p-C0R15 or - ( CH2) q0H or, if R3, R5 and R6 are hydrogen, R ^ is additionally a group of the formula III

1008373 1 *, .....

^ 17 wherein Rj is defined as shown above for n = 1, R6 is hydrogen or a group of the formula IV

15 J

RkAX YY R, (IV) r3

20 X.

where R *, is not a group of formula III and R 1 is defined as shown above for n = 1, R 7, Rgl Rg, R10 and Rn independently hydrogen, halogen, hydroxyl, C 1 -C 23 alkyl, C 2 -C 25 alkyl interrupted by oxygen, sulfur, or N-Rjj; C 1 -C 25 alkoxy, C 2 -C 25 alkoxy interrupted by oxygen, sulfur or N-Rli (; C 1 -C 8 alkylthio, C3-C25 alkenyl, C3-C25 alkenyloxy, C3-C25 alkynyl, C3-C25 alkynyloxy C7-C9 phenylalkyl, C7-C9 phenyl alkoxy, unsubstituted or C 1 -C 9 alkyl substituted phenyl, unsubstituted or C 1 -C 1 alkyl substituted phenoxy, unsubstituted or C 1 -C 8 alkyl substituted C 5 -C 8 cycloalkyl; unsubstituted or C 1 -C 7 alkyl substituted C 5 -C 8 cycloalkoxy, di (C 1 -C 8 alkyl) amino, C 1 -C 25 alkanoyl, C 3 -C 25 alkanoyl interrupted by oxygen, sulfur, or N-R 14; C 1 -C 4 alkanoyloxy, C3-C25 alkanoyloxy which is 40 | 1008373 5 interrupted by oxygen, sulfur or N-Rh 2, C 1 -C 25 alkanoylamino, C3-C25 alkenoyl, C3-C23 alkenoyl interrupted by oxygen, sulfur or

5 I

N-Rj * ,; C3-C25alkenoyloxy, C3 -C25alkenoyloxy interrupted by oxygen, sulfur or N-Rlit; C8-C9 cycloalkylcarbonyl, C6-C9 cycloalkyl-

10 I

carbonyloxy, benzoyl or benzoyl substituted with C 1 -C 12 alkyl; benzoyloxy or benzoyloxy substituted with C 1 -C 18 alkyl;

R18 0 r20 r21 15 -0-C-C-R, c or-0-C-C-0-R2, are, or else, in formula

I II

Rig R ^ 22 II, the groups R? and R8 or the groups R8 and Rn, together with the carbon atoms to which they are attached, form a benzo ring, R12 and R13 are independently unsubstituted or C 1 -C 2 alkyl-substituted phenylene or naphthylene,

Rj /, is hydrogen or C 1 -C 8 alkyl, R 24 is Γ-1 r + ^ 25 hydroxyl, -q -J-m · C 1 -Cl 8 alkoxy or -N, r 23

R 16 and R 7 are independently hydrogen, CF 3, C 1 -C 6 alkyl or phenyl, or R 6 and R 17, together with the C atom to which they are attached, form a C 5 -C 8 cycloalkylidene ring that is unsubstituted or 1-3 times is substituted with C 1 -C 2 alkyl;

R 18 and R 19 are independently hydrogen, C 1 -C 2 alkyl, or phenyl, R 20 is hydrogen or C 1 -C 2 alkyl, R 21 hydrogen, unsubstituted or C 1 -C 2 alkyl substituted phenyl; C 1 -C 25 alkyl, C 2 -C 25 alkyl interrupted by oxygen, sulfur, or N-R 2 alkyl; C7-C9 phenylalkyl which is unsubstituted or which is substituted 1-3 times with C 1 -C 2 alkyl on the phenyl group; C7-C25 phenylalkyl which is unsubstituted or which is substituted 1-3 times on the phenyl group with C 1 -C 2 alkyl and is interrupted by oxygen, sulfur or 1008373 6 N-Rn, or else the groups R20 and R21, together with the carbon atoms to which they are attached form a C5-C12 cycloalkylene ring which is unsubstituted or substituted 1-3 times with -C18 alkyl; R22. hydrogen or C 1 -C 2 alkyl, R 23 is hydrogen, C 1 -C 20 alkanoyl, C3-C25 alkenoyl, C3-C25 alkanoyl interrupted by oxygen, sulfur or N-Rli (; C3-C25 alkanoyl which is | substituted with a di (C 1 -C 6 alkyl) phosphonate group; C 1 -C 9 cycloalkyl carbonyl, thenoyl, furoyl, benzoyl or C 1 -C 12 alkyl substituted benzoyl; 15 un PHs CH3 H3Cv / H3Cv / 3 I / ^ CCH3. h JrCc ">.

-C C 5 H 10 OH c-CH 2 -S-CH 2 -V-OH

* 26 R26 20 CHa "h3c / o II CH3OO II / r \ K II" ii - c-CH-C-- -CR-C-R2e or -C-R-25 ch3 rm LJ 2, is, R2 and R25 independently of one another are hydrogen or C 1 -C 18 alkyl, R 26 is hydrogen or C 1 -C 8 alkyl, R 27 is a direct bond, C 1 -C 18 alkylene, C 2 -C 18 alkylene interrupted by oxygen, sulfur or N-R 14 C 2 -C 18 alkenylene, C 2 -C 20 alkylidene, C7-C20 phenylalkylidene, C5-C8 cycloalkylene, C7-C8 bicycloalkylene, unsubstituted or C 1 -C 18 alkyl-substituted phenylene or 1 or 8 00 373, 7 H2ii R28 is hydroxyl, -Ο * - ΜΓ +. C, -Cl8 alkoxy or -N,

5 L r J I

R * 5 0

I II

R29 is oxygen, -NH- or N-C-NH-R30,

10 I

R 30 is C 1 -C 18 alkyl or phenyl, R 31 is hydrogen or C 1 -C 18 alkyl, M is an r-worthy metal cation, X is a direct bond, oxygen, sulfur or -NR31-, 15 n is 1 or 2, p 0, 1 or 2, q is 1, 2, 3. 4, 5 or 6, r is 1, 2 or 3 and s is 0, 1 or 2.

Unsubstituted or naphthyl substituted by C 1 -C 4 alkyl, C 1 -C 8, alkoxy, C 1 -CT, alkylthio, hydroxyl, halogen, amino, C 1 -C 7 alkylamino, phenylamino or diiC 1 -C 7 alkyl) amino, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo [b] thienyl, naphto [2,3-b] thienyl, thiantrenyl, dibenzofuryl, chromenyl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidynyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazololol, quininyl, quininyl, quininyl, quinolinyl For example, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, bi-phenyl, terphenyl, fluorenyl or phenoxazinyl is 1-naphthyl, 2-naphthylamino -4-naphthyl, 1-methylnaphthyl, 2-methylnaphthyl, 1-methoxy-2-naphthyl, 2-methoxy-1-naphthyl, 1-dimethylamino-2-naphthyl, 1,2-dimethyl-4-naphthyl, 1 , 2-dime thyl-6-naphthyl, 1,2-dimethyl-7-naphthyl, 1,3 "dimethyl-6-naphthyl, 1,4-dimethyl-6-naphthyl, 1,5" dimethyl-2-naphthyl, 1,6 -dimethyl-2-naphthyl, 1-hydroxy-2-naphthyl, 2-hydroxy-1-naphthyl, 1,4-di-hydroxy-2-naphthyl, 7 "phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl .3 "benzo- [bjthienyl, 5" benzo [b] thienyl, 2-benzo [b] thienyl, 4-dibenzofuryl, 4,7-dibenzofuryl, 4-methyl-7 "dibenzofuryl, 2-xanthenyl, 8-methyl- 2-xanthe-40-nyl, 3-xanthenyl, 2-phenoxathiinyl, 2,7-phenoxathiinyl, 2-pyrrolyl, 3 "pyrrolyl, 5" methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 2-methyl-4 - 1008373 8 imidazolyl, 2-ethyl - ^ - imidazolyl, 2-ethyl-5-imidazolyl, 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl-pyrazolyl, 2-pyrazinyl, 5.6-dimethyl-2 pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindolyl, 1-methyl-2-indolyl, 1-methyl-3-indolyl, 1,5-dimethyl-2-indolyl 1,5-methyl-3-indazolyl, 2,7-dimethyl-8-purinyl, 2-methoxy-7-methyl-8-purinyl, 2-quinolizinyl, 3 "isoquinolyl, 6-isoquinolyl, 7" isoquinolyl, isoquinolyl, 3-ni ethoxy-6-isoquinolyl, 2-quinolyl, 6-quinolyl, 7-quinolyl, 2-methoxy-3-quinolyl, 2-methoxy-6-quinolyl, 6-phthalazinyl, 7 "f-lazinyl, 1-methoxy-6- phthalazinyl, 1,3-dimethoxy-phthalazinyl, 1,8-10 naphthyridin-2-yl, 2-quinoxalinyl, 6-quinoxalinyl, 2,3 "dimethyl-6-quinoxalinyl, 2,3-dimethoxy-6-quinoxalinyl , 2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino-6-quinazolinyl, 3-cinnolinyl, 6-cinnolinyl, 7 "cinnolinyl, 3-nonhoxy-7-cinnolinyl, 2-pteridinyl, 6-pteridinyl, 7-pteridinyl 6,7-dimethoxy-2-pteridinyl, 2-carbazolyl, 3-carbazolyl, 9-15 methyl-2-carbazolyl, 9-methyl-3-carbazolyl, p-carboline-3-yl. 1-methyl-3-carbolin-3-yl, 1-methyl-β-carbolin-6-yl, 3-phenanthridinyl, 2-acridinyl, 3-acridinyl, 2-perimidinyl, 1-methyl-5-perimidinyl, 5 ~ phenanthrolinyl, 6-phenanthrolinyl, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazinyl, 3-phenothiazinyl, 20 10-methyl-3-phenothiazinyl, 3-isoxazolyl, ^ isoxazolyl, 5-isoxazolyl, 4-methyl-3-furazanyl, 2-phenoxazinyl or 10-methyl-2-phenoxazinyl.

Particular preference is given to unsubstituted or substituted by naphthyl, phenanthryl, anthryl, 5,6,7,8, C 1 -C 7 alkyl, C 1 -C 7 alkoxy, C 1 -C 6 alkylthio, hydroxyl, phenylamino or diiC 1 -C 1, alkyl) -amino. -tetrahydro-2-25 naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo [b] thienyl, naphtho [2,3_b] thienyl, thiantrenyl, dibenzofuryl, chromyl, xanthenyl, phenoxathiinyl, isoindolyl , indolyl, phenothiazinyl, biphenyl, terphenyl, fluorenyl or phenoxazinyl, for example 1-naphthyl, 2-naphthyl, 1-phenyl-amino-naphthyl, 1-methylnaphthyl, 2-methylnaphthyl, 1-methoxy-2-naphthyl, 2- 30-methoxy-1-naphthyl, 1-dimethylamino-2-naphthyl, 1,2-dimethyl-4-naphthyl, 1,2-dimethyl-6-naphthyl, 1,2-dimethyl-7-naphthyl, 1,3-dimethyl -6-naphthyl, 1,4-dimethyl-6-naphthyl, 1,5-dimethyl-2-naphthyl, 1,6-dimethyl-2-naphthyl, 1-hydroxy-2-naphthyl, 2-hydroxy-1-naphthyl 1,1,6-dihydroxy-2-naphthyl, 7 "phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl, 3" benzo [b] thienyl, 5-benzoien [2] benzo [b] thienyl , -dibenzofuryl, 4,7-dibenzofuryl, 4-methyl-7-dibenzofuryl, 2-xant henyl, 8-methyl-2-xanthenyl, 3-xanthenyl, 2-pyrrolyl, 3-pyrrolyl, 2-phenothiazinyl, 3 "phenothiazinyl, 10-methyl-3-phenothiazinyl.

> ^ Λ 1008373 9

For example, halogen is chlorine, bromine or iodine, chlorine is preferred.

Alkanoyl of up to 25 carbon atoms is a branched or unbranched group, for example, formyl, acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undeca-noyl, dodecanoyl, tridecanoyl, tetradecanoyl, pent heptadecanoyl, octadecanoyl, eicosanoyl or docosanoyl. Alkanoyl with 2-18, especially 2-12, for example 2-6 carbon atoms is preferred. Acetyl is particularly preferred.

For example, C 2 -C 25 alkanoyl substituted with a diiC 1 -C 8 alkyl) phosphonate group is (CH3CH20) 2P0CH2C0-, (CH30) 2P0CH2C0-, (CH3CH2CH2CH20) 2POCH2CO-, (CH3CH20) 2P0CH2CH2C0-, (CH30) ) 2poch2ch2co-, (ch3ch2o) 2P0 (CH2) * co-, (CH3CH20) 2P0 (ch2) 8co- or (CH3CH20) 2P0 (CH2) 17C0-.

Alkanoyl of up to 25 carbon atoms is a branched or unbranched group, for example formyloxy, acetoxy, propionyloxy, buta-noyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nona-noyloxy, decanoyloxy, undecanoyloxy, dodecanoylocanloxy, dodecanoylocanloxy , heptadecanoyloxy, octadecanoyloxy, eicosanoyloxy or docosanoyloxy. Alkanoyloxy with 2 -18, especially 2-12, for example 2-6 carbon atoms is preferred. Acetoxy is particularly preferred.

Alkenoyl of 3 ~ 25 carbon atoms is a branched or unbranched group, for example propenoyl, 2-butenoyl, 3-butenoyl, isobutenoyl, n-2,4-pentadienoyl, 3-nonhyl-2-butenoyl, n-2-octenoyl, n-2 dodecenoyl, isododecenoyl, oleoyl, n-2-octadecanoyl or n-2-octadecenoyl. Alkenoyl with 3-18, especially 3 ~ 12, for example 3 "6, especially 3" carbon atoms is preferred.

C3-C25alkenoyl interrupted by oxygen, sulfur or N-R 2 is, for example, CH 3 OCH 2 CH 2 CH = CHCO- or CH 3 OCH 2 CH 2 OCH = chco-.

Alkenoyloxy of 3-25 carbon atoms is a branched or unbranched group, for example propenoyloxy, 2-butenoyloxy, 3 "butenoyloxy, iso-35 butenoyloxy, nP. -Pentadienoyloxy, 3-ethyl-2-butenoyloxy, n-2-oc-tenoyloxy , n-2-dodecenoyloxy, isododecenoyloxy, oleoyloxy, n-2-octa-decenoyloxy or n-4-octadecenoyloxy Alkenoyloxy with 3-18, in particular 3 "12, for example 3" 6, in particular 3-14 carbon atoms is preferred .

1 008373 10

For example, CH30CH2CH2CH = CHC00- or CH3OCH2CH2OCH = CHCOO- by interrupted C3 -C25 alkenoyloxy by oxygen, sulfur or N-Rli.

5 I

C3-C25 alkanoyl interrupted by oxygen, sulfur or N-R 1 is, for example, ch3-o-ch2co-, ch3-s-ch2co-, ch3-nh-ch2co-, ch3-n (ch3) -ch2co-, ch3- o-ch2ch2-o-ch2co-, ch3- (0-CH2CH2-) 20-CH2C0-, CH3- (0-CH2CH2-) 30-CH2C0- 10 or ch3- (0-CH2CH2-);, 0-CH2C0- .

For example, C3-C25 alkanoyloxy interrupted by oxygen, sulfur, or N-Rj * is CH3-O-CH2C00-, CH3-S-CH2C00-, CH3-NH-CH2C00-, 15 CH3-N (CH3) -CH2C00-, ch3 -o-ch2ch2-o-ch2coo-, CH3- (0-CH2CH2-) 20-CH2C00-, CH3- (0-CH2CH2-) 30-CH2C00- or CH3- {0-CH2CH2-) 40-0Η2000-.

C6-C8 cycloalkylcarbonyl is, for example, cyclohexylcarbonyl, cycloheptylcarbonyl or cyclooctylcarbonyl. Cyclohexylcarbonyl is preferred.

C 1 -C 9 cycloalkylcarbonyloxy is, for example, cyclohexylcarbonyloxy, cycloheptylcarbonyloxy or cyclooctylcarbonyloxy. Cyclohexylcarbonyloxy is preferred.

Benzoyl substituted by C 1 -C 12 alkyl, which preferably contains 1-3, especially 1 or 2 alkyl groups, is for example o-, m- or p-25 methylbenzoyl, 2,3-dimethylbenzoyl, 2,4-dimethylbenzoyl, 2 .5-dimethyl-benzoyl, 2,6-dimethylbenzoyl, 3,3-dimethylbenzoyl, 3,5-dimethylbenzoyl, 2-methyl-6-ethylbenzoyl, 4-tert-butylbenzoyl, 2-ethylbenzoyl, 2,4,6-trimethylbenzoyl 2,6-dimethyl-4-tert-butylbenzoyl or 3.5 "di-tert-butylbenzoyl. Preferred substituents are C 1 -C 6 alkyl, especially C 1 -C 8 alkyl.

Benzoyloxy, which is preferably 1-3, especially 1 or 2, alkyl groups substituted by C 1 -C 12 alkyl is, for example, o-, m- or p-methylbenzoyloxy, 2,3-dimethylbenzoyloxy, 2,4-dimethylbenzoyloxy, 2,4 5-dimethylbenzoyloxy, 2,6-dimethylbenzoyloxy, 3,4-dimethylbenzoyl-oxy, 3 * 5-dimethylbenzoyloxy, 2-methyl-6-ethylbenzoyloxy, 4-tert-butyl-benzoyloxy, 2-ethylbenzoyloxy, 2,4,6 trimethylbenzoyloxy, 2,6-dimethyl-4-tert-butylbenzoyloxy or 3,5-di-tert-butylbenzoyloxy. Preferred substituents are C 1 -C 8 alkyl, especially C 1 -C 8 alkyl.

40 Alkyl of up to 25 carbon atoms is a branched or unbranched group, 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 "tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, 5 n-octyl, 2-ethylhexyl, 1,1 , 3-trimethylhexyl, 1,1,3,3 "tetramethyl-pentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3 * 3.5.5" hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hepta-decyl , octadecyl, eicosyl or docosyl. For example, one of the preferred meanings of R 2 and R / is C 1 -C 18 alkyl. A particularly preferred meaning of R / is 0.06 alkyl.

Alkenyl of 3 "25 carbon atoms is a branched or unbranched group, for example propenyl, 2-butenyl, 3" butenyl, isobutenyl, n-2, - pentadienyl, 3-roethyl-2-butenyl, n-2-octenyl, n- 2-dodecenyl, isodode-cenyl, oleyl, n-2-octadecenyl or n-octadecenyl Alkenyl with 3 "18, in particular 3 ~ 12, for example 3" 6, in particular 3-i + carbon atoms is preferred.

Alkenyloxy of 3 "25 carbon atoms is a branched or unbranched group, for example propenyloxy, 2-butenyloxy, 3" butenyloxy, iso-butenyloxy, n-2,1 (pentadienyloxy, 3-methyl-2-butenyloxy, n-2-octenyl) -20 oxy, n-2-dodecenyloxy, isododecenyloxy, oleyloxy, n-2-octadecenyloxy or n-4-octadecenyloxy Alkenyloxy with 3-l8, especially 3 ~ 12, for example 3 "6, especially 3" ^ carbon atoms are preferred.

Alkynyl of 3-25 carbon atoms is a branched or unbranched group, for example propynyl (-CH2-CsCH), 2-butynyl, 3-butynyl, n-2-octynyl or n-2-dodecynyl. Alkynyl with 3 "18, especially 3" 12, for example 3 "6, especially 3" carbon atoms is preferred.

Alkynyloxy with 3 "25 carbon atoms is a branched or unbranched group, for example propynyloxy {-0CH2-C2CH), 2-butynyloxy. 3-butynyloxy, n-2-octynyloxy or n-2-dodecynyloxy. Alkynyloxy with 3 ~ 18 especially 3 "12, for example 3" b, especially 3 "carbon atoms are preferred.

C3-c25 alkyl interrupted by oxygen, sulfur or NR, * is, for example, ch3-o-ch2-, ch3-s-ch2-, ch3-nh-ch2-, CH3-N {CH3) -CH2-, CH3-0 -CH2CH2 - <) - CH2-, CH3- (0-CH2CH2-) / ΚΗ2-, CH3- (0-CH2CH2-) 30-CH2- or CH3- (0-CH2CH2 -) / 10-CH2-.

C7-C9 phenylalkyl is, for example, benzyl, α-methylbenzyl, α, α-1008373 12 dimethylbenzyl or 2-phenylethyl. Benzyl and α, α-dimethylbenzyl are preferred.

C 7 -C 8 phenylalkyl which is unsubstituted or substituted 1-3 times with C 1 -C 4 alkyl on the phenyl group is, for example, benzyl, a-5 methylbenzyl, α, α-dimethylbenzyl, 2-phenylethyl, 2-methylbenzyl, 3-methylbenzyl, --methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzyl or--tert-butylbenzyl. Benzyl is preferred.

C 1 -C 25 phenylalkyl which is unsubstituted or substituted 1-3 times with C 2 -C 8 alkyl on the phenyl group and which is interrupted

10 I

by oxygen, sulfur or NR ^ is a branched or unbranched group, for example phenoxymethyl, 2-methylphenoxymethyl, 3-methylphenoxymethyl, 4-methylphenoxymethyl, 2, H-dimethylphenoxymethyl, 2,3-dimethylphenoxy-methyl, phenylthiomethyl, N-methyl- N-phenylmethyl, N-ethyl-N-phenyl-methyl, 4-tert-butylphenoxymethyl, tert-butylphenoxyethoxymethyl, 2, di-tert-butylphenoxymethyl, 2,4-di-tert-butylphenoxyethoxymethyl, phenoxyethoxyethoxyethoxymethyl, benzyloxymethyl, benzyloxyethoxymethyl, N-benzyl-N-ethylmethyl or N-benzyl-N-isopropylmethyl.

C7-C9 phenylalkoxy is, for example, benzyloxy, α-methylbenzyloxy, α, α-dimethylbenzyloxy or 2-phenylethoxy. Benzyloxy is preferred.

Phenyl substituted with C 1 -C 1 alkyl, preferably 1-3. in particular contains 1 or 2 alkyl groups, for example is o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2.ij-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3. dimethylphenyl 3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl or 2,6-diethylphenyl.

Phenoxy-substituted phenoxy which preferably contains 1-3, especially 1 or 2 alkyl groups, is for example o-, m- or p-methylphenoxy, 2,3-dimethylphenoxy, 2,2-dimethylphenoxy, 2 5-dimethyl-30-phenoxy, 2,6-dimethyl-phenoxy, 3-dimethyl-phenoxy, 3.5-dimethyl-phenoxy, 2-methyl-6-ethyl-phenoxy, ή-t-butyl-phenoxy, 2-ethyl-phenoxy or 2,6-diethyl-phenoxy.

Unsubstituted or C 1 -C 8 alkyl substituted C 5 -C 8 cycloalkyl is, for example, cyclopentyl, methylcyclopentyl, dimethylcyclo-pentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethyl-cyclohexyl, tert-butylcyclohexyl, cycloheptyl or cyclooctyl. Cyclohexyl and tert-butylcyclohexyl are preferred.

Unsubstituted or C 1 -C 8 alkyl-substituted C 5 -C 8 cycloalkoxy is, for example, cyclopentoxy, methylcyclopentoxy, dimethyl 1008373 13 cyclopentoxy, cyclohexoxy, methylcyclohexoxy, diraethylcyclohexoxy, trimethylcyclohexoxy, tert-butylcycloheoxy, cycloheptoxy. Cyclohexoxy and tert-butylcyclohexoxy are preferred.

Alkoxy of up to 25 carbon atoms is a branched or unbranched group, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. Alkoxy with 1-12, especially 1-8, for example 1-6 carbon atoms is preferred.

10 |

C3-C23 alkoxy interrupted by oxygen, sulfur or N-Rl4 is, for example, ch3-o-ch2ch2o, ch3-s-ch2ch2o, ch3-nh-ch2ch2o, ch3-n (ch3) -ch2ch2o, ch3-o- ch2ch2-o-ch2ch2o, ch3- (0-CH2CH2-) 20-CH2CH2O-, 15 CH3- (0-CH2CH2-) 30-CH2CH2O- or ch3- (o-ch2ch2-) ^ ok: h2ch2o.

Alkylthio of up to 25 carbon atoms is a branched or unbranched group, for example, methylthio, ethylthio, propylthio, iso -propylthio, n-butylthio, isobutylthio, pentylthio, isopentylthio, hexylthio, heptylthio, octylthio, decylthio, tetradecylthyl, tetradecylthio. Alkylthio with 1-12, especially 1-8, for example 1-6 carbon atoms is preferred.

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

Di (C 1 -C 3, alkyl) amino also means that the two groups are independently branched or unbranched, for example dimethylamino, methyl ethyl hylamino, diethylamino, methyl n-propylamino, methyl isopropyl amino, methyl n-butylamino, methyl isobutylamino ethylisopropylamino, ethyl-n-butylamino, ethylisobutylamino, ethyl-tert-butylamino, di-ethylamino, diisopropylamino, isopropyl-n-butylamino, isopropyliso-butylamino, di-n-butylamino or diisobutylamino.

Alkanoylamino of up to 25 carbon atoms is a branched or unbranched group, for example formylamino, acetylamino, propionylamino, butanoylamino, pentanoylamino, hexanoylamino, heptanoylamino, 35 octanoylamino, nonanoylamino, decanoylamino, undecanoyecino, dodeca-noylamoylamino, dodecanoylamino, heptadecanoylamino, octadecanoylamino, eicosanoyl-amino or docosanoylamino. Alkanoylamino with 2-18, especially 2-12, for example 2-6 carbon atoms is preferred.

1008373 14

C 1 -C 8 alkylene is a branched or unbranched group, for example methylene, ethylene, propylene, trimethylene, tetramethylene, penta-methylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene or octadecamethylene alkylene, especially Cj-Cg alkylene the preference.

An alkyl-substituted C5 -C12 cycloalkylene ring, which preferably contains 1-3, especially 1 or 2, branched or unbranched alkyl groups are, for example, cyclopentylene, methylcyclopentylene, dimethylcyclopentylene, cyclohexylene, methylcyclohexylene, dimethylcyclohexylene, trimethylcyclohexylene, tert-butyl hexylene, cycloheptylene, cyclooctylene or cyclodecylene. Cyclohexylene and tert-butylcyclohexylene are preferred.

C 1 -C 18 alkylene interrupted by oxygen, sulfur or N-R 2 is

15 I

example -CH2-0-CH2-, -CH2-S-CH2-, -CH2-NH-CH2-, -CH2-N (CH3) -CH2-, -CH2-0-CH2CH2-0-CH2-, -CH2 - (0-CH2CH2-) 2o-ch2-, -CH2- (0-CH2CH2-) 3o-ch2-, -ch2- {o-CH2CH2-) ^ 0-CH2- or -ch2ch2-s-ch2ch2-.

C2-Cl8 alkenylene is, for example, vinylene, methyl vinylene, oc-20 tenylethylene or dodecenylethylene. C2-Ce alkenylene is preferred.

Alkylidene of 2-20 carbon atoms is, for example, ethylidene, propylidene, butylidene, pentylidene, 4-roethylpentylidene, heptylidene, nonylidene, tridecylidene, nonadecylidene, 1-methylethylidene, 1-ethylpropylidene or 1-ethylpentylidene. C2-C8 alkylidene 25 is preferred.

Phenylalkylidene with Ί-20 carbon atoms is, for example, benzylidene, 2-phenylethylidene or 1-phenyl-2-hexylidene. C7-C9 phenylalkylidene is preferred.

C5-C8 cycloalkylene is a saturated hydrocarbon group with two free valencies and at least one ring unit and is, for example, cyclopentylene, cyclohexylene, cycloheptylene or cyclooctylene. Cyclohexylene is preferred.

C7-Ce bicycloalkylene is, for example, bicycloheptylene or bi-cyclooctylene.

Unsubstituted or C 1 -C 4 alkyl-substituted phenylene or naphthylene is, for example, 1,2-, 1,3 "> 1,4-phenylene, 1,2-, 1,3" <1,4-, 1.6 -, 1,7-, 2,6- or 2,7-naphthylene. 1,4-phenylene is preferred.

A C 1 -C 8 alkyl substituted C 5 -C 8 cycloalkylidene ring, preferably containing 1-3, especially 1 or 2, branched or unbranched 1008373 alkyl groups, for example, cyclopentylidene, methylcyclopentylidene, dimethylcyclopentylidene, cyclohexylidene, methylcyclohexylidene, dimethylcyclohexylidene, trimethylcyclohexylidene, tert-butylcyclohexylidene, cycloheptylidene or cyclooctylidene. Cyclo-5 hexylidene and tert-butylcyclohexylidene are preferred.

A monovalent, bivalent or trivalent cetal cation is preferably an alkali metal, alkaline earth metal or aluminum cation, for example Na *, K \ Mg **, Ca ** or Al ***.

Compositions of interest include those comprising as component (b) at least one compound of the formula I wherein, when η is 1, R 1 is unsubstituted phenyl or phenyl substituted in the para position with C 1 -C18 alkylthio or di (C 1 -C 18 alkyl) amino; mono- or penta-substituted alkylphenyl having a total of no more than 18 carbon atoms in the 1-5 alkyl substituents; or unsubstituted or substituted with C 1 -C 8, alkyl, C 1 -C 3, alkoxy, C 1 -C 11 alkylthio, hydroxyl or amino naphthyl, biphenyl, terphenyl, phenanthryl, anthryl, fluorenyl, carbazolyl, thienyl, pyrrolyl, phenothiazinyl or 5.6 7.8-tetrahvdronaphthyl.

Preference is given to compositions comprising as component 20 (b) at least one compound of the formula I, wherein, when n is 2,

Rj is -R] 2 -X-Rj3-, R12 and Rj3 are phenylene, X is oxygen or -NR3j- and R31 is alkyl.

Preference is also given to compositions comprising as component (b) at least one compound of the formula I, wherein, when n is 1, R) is unsubstituted or with C 1 -C 1 / alkyl, C 1 -C /, alkoxy, C 1 -C /, alkylthio, hydroxyl, halogen, amino, C 1 -C /, alkylamino or di (C) -C /, alkyl) amino substituted naphthyl, phenanthryl, thienyl, dibenzofuryl, carbazolyl, fluorenyl or a group of the formula II is 1008373 16 -

5 T

Re R7, R8, R9, Rjo and Ru independently of each other are hydrogen, chlorine, bromine, hydroxyl, C 1 -C 18 alkyl, C 2 -C 18 alkyl interrupted by oxygen or sulfur; C 1 -C 18 alkoxy, C 2 -C 18 alkoxy interrupted by oxygen or sulfur; C 1 -C 8 alkylthio, C 3 -C 8 alkenyloxy, C 3 -C 12 alkynyloxy, C 1 -C 9 phenylalkyl, C 7 -C 9 phenylalkoxy, unsubstituted or C 1 -Cb alkyl substituted phenyl; phenoxy, cyclohexyl, C 1 -C 8 cycloalkoxy, C 1 -C 15, alkylamino, di (C 1 -C 4 alkyl) amino, C 1 -C 12 alkanoyl, C 3 -C 12 alkanoyl interrupted by oxygen or sulfur; C 1 -C 12 alkanoyloxy, C 3 -C 12 alkanoyloxy interrupted by oxygen or sulfur; C 1 -C 12 alkanoyl amino, C 3 -C 12 alkenoyl, C 3 -C 12 alkenoyloxy, cyclohexylcarbonyl, cyclohexylcarbonyloxy, benzoyl, or C 1 -C 2 alkyl substituted benzoyl; Benzoyloxy or C 1 -C 3 alkyl substituted benzoyloxy;

Ri8 0 R20 ^ 21 - 0 - C - C - Ric or-0-C-C-0-R2, are, or else, in formula

I II

R19 H R22 II, the groups R7 and R8 or the groups R8 and Ra, together with the carbon atoms to which they are bonded, form a benzo ring, R24 is 30 R 5 hydroxyl, C 1 -C 12 alkoxy or -N,

R 18 and R 19 are independently hydrogen or C 1 -C 18 alkyl, R 20 is hydrogen, R 21 is hydrogen, phenyl; C 1 -C 18 alkyl, C 2 -C 18 alkyl interrupted by oxygen or sulfur; C7-C9 phenylalkyl, C7-C18 phenylalkyl which is unsubstituted or substituted on the phenyl group 1-3 times with Cx-C 1-4 alkyl and is interrupted by oxygen or sulfur, or else the groups R20 and R21, together with the carbon atoms to which they are bonded form a cyclohexylene ring which is unsubstituted or substituted 1-3 times with C 1 -C * alkyl; 1008373 17 R 22 is hydrogen or C 1 -C 8 alkyl, R 23 hydrogen, C 1 -C 18 alkanoyl, C 3 -C 18 alkenoyl, C 3 -C 12 alkanoyl interrupted by oxygen or sulfur; C3 -C12 alkanoyl substituted with a di (C1 -C6 alkyl) phosphonate group; C6-C9 cycloalkylcarbonyl, 5-benzoyl, H3C, CH3 o II M CH> -C-C, Hs-^ λ-ΟΗ '10 R36 CH. Γ CH3 H, CV / 3 H3Cv / yy ri "™ 3 II / - (C" CH3 -C-CH — S — CH2— '-c-CHZ — C-- 15 ”R26 ch3 r26 lj 2 0 0 -0 II II or II C R27 C R2a CR ^ ~ Rjo 20, R2i, and R2- independently of one another are hydrogen or C 1 -C 12 alkyl, R 26 is hydrogen or C 1 -C *, alkyl, R 27 C 1 -C 12 alkylene, C2- C8 is alkenylene, C2-C8 alkylidene, C7-C12 phenyl-alkylidene, C5-C8 is cycloalkylene or phenylene, R2 is R2 * R28 hydroxyl, C1-C2 alkoxy or -N, r25 is 30 R29 oxygen or -NH-, R30 is CrCl8 is alkyl or phenyl and s is 1 or 2.

Likewise, preference is given to compositions comprising as component (b) at least one compound of the formula I, wherein, when η is 1,

R 1 phenanthryl, thienyl, dibenzofuryl, unsubstituted or C 1 -C 3 alkyl substituted carbazolyl; or is fluorenyl; or Rj is a group of formula II

1008373 18 - R8 R7, Rg, R8, R10 and Rn independently of each other hydrogen, chlorine, hydroxyl, C 1 -C 18 alkyl, C 1 -C 18 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkenyloxy, Cg -C /, alkynyloxy, phenyl, benzoyl benzoyloxy or R20 R21 -0-CC-0-R23,

15 II

H R22 R20 is hydrogen, R21 is hydrogen, phenyl or C 1 -C 18 alkyl, or else the groups R20 and R21, together with the carbon atoms to which they are attached, form a cyclo-20 hexylene ring that is unsubstituted or 1-3 times is substituted with C 1 -C 18 alkyl, R 22 is hydrogen or C 1 -C * alkyl, and R 23 is hydrogen, C 1 -C 12 alkanoyl or benzoyl.

Particular preference is given to compositions comprising as component (b) at least one compound of the formula I, wherein, when η is 1,

Ry, R8, Rg, R10 and Rn are independently hydrogen, C1 -C1 alkyl, C1 -C1, alkylthio or phenyl.

Of particular interest are compositions comprising, as component (b), at least one compound of the formula I, wherein R 2, R 3, R 1, and R 5 independently of each other are hydrogen, chlorine, C 1 -C 18 alkyl, benzyl, phenyl, C 1-6. C 1 -C 20 cycloalkyl, C 1 -C 18 alkoxy, C 1 -C 18 alkylthio, C 1 -C 18 alkanoyloxy, C 1 -C 18 alkanoylamino, C 3 -C 18 alkenoyloxy or benzoyloxy; or else the groups R2 and R3 or the groups R3 and R4 or the groups R4 and R5, together with the carbon atoms to which they are attached, form a benzo ring, wherein R /, additionally - (CH2) p-C0R15 or - (CH2 q0H is or, when R3, R5 and Rg are hydrogen, R ^ is additionally a group of formula III, 1008373 19 R2ii Rc hydroxyl, C, -C12 alkoxy or -N, 5 R25

R 16 and R 17 are methyl groups or, together with the C atom to which they are attached, form a C 3 -C 8 cycloalkylidene ring which is unsubstituted or is substituted 1-3 times with C 1 -C 18 alkyl, R 2 (t and R 2 - independently of each other is hydrogen or C 1 -C 12 alkyl, 10 p is 1 or 2 and q is 2, 3, 4, 5 or 6.

Also of particular interest are compositions comprising as component (b) at least one compound of the formula I wherein at least two of the groups R 2, R 3, R 1, and R 3 are hydrogen.

Of special interest are compositions comprising as component (b) at least one compound of the formula I, wherein R 3 and R 5 are hydrogen.

Of particular interest are compositions comprising as component (b) at least one compound of the formula I wherein R 2 is C 1 -C 6 alkyl, R 3 is hydrogen,

Rit is Cj-Cfc alkyl, or if Rj is hydrogen, Rj is additionally a group of formula III, R3 is hydrogen and Rj6 and Rj-, together with the C atom to which they are attached, form cyclohexylidene .

The following compounds are examples of the benzofuran-2-on type which are particularly suitable as component (b) in the new composition: 3 "[^" (2-acetoxyethoxy) phenyl] ~ 5,7-di-tert-butylbenzo - furan-2-one; 5.7 "di-tert-butyl-3- [i + - (2-stearoyloxyethoxy) phenyl] benzo-furan-2-one; 3,3'-bis [5,7-di-tert-butyl -3 - (^ - [2-hydroxyethoxy] -phenyl) benzofuran-2-one], 5,7 "di-tert-butyl-3 - (^ - ethoxyphenyl) benzofuran-2-one; 3" (4-acetoxy -3,5-dimethylphenyl) -5Y-di-tert-butylbenzofuranone; 3 "(3> 5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butyl-benzofuran-2-35 one; 5.7-di-tert-butyl-3-phenyl-benzofuran-2-one; 5.7-di-tert -butyl-3- (3-dimethylphenyl) benzofuran-2-one, 5,7-di-tert-butyl-3- (2,3-dimethylphenyl) benzofuran-2-one.

Also of special interest are compositions comprising as component (b) at least one compound of formula V 1008373

O

Y tY 'm

5 / L · JL · JL · JL

^ 3 1 ^ ^ 5 R4 R8 10 where R 2 is hydrogen or C 1 -C 6 alkyl, R 3 is hydrogen,

R 1 is hydrogen or C 1 -C 6 alkyl, 15 is R, hydrogen, R 71 is R 8. R9. R10 and Ru independently of one another are hydrogen, C 1 -C 2 alkyl or C 1 -C 2 alkoxy, with the proviso that at least two of the groups R7, R8, R9, R10 or Ru are hydrogen.

Very particular preference is given to compositions comprising as component (b) at least one compound of the formula Va or Vb

O O

/ C '^ YYK-V # kT ^ CH = 25 HjC ΥγΙ I ^ jl ^ HsC l ^ yj H3C — C — CH3 H3C — C — CH3 ch3 ch3 30 (Va) (Vb) or a mixture of the two compounds with include the formula Va and Vb.

The benzofuran-2-on type compounds as component (b) in the new composition are known from the literature and their preparation is described, for example, in the following US patents: * <325863. 4388244, 5175312, 5252643, 5216052, 5369159,, 1008373 21 5 ^ 88117, 5356966, 5367008, 5428162, 5428177, or 5516920.

Of particular interest are compositions comprising as component (c) at least one compound from the group of the organic phosphites or phosphonites of formulas 1 to 7 5 r η / O_R '* O-R', (1) R ' -y — PN A'— X '· —P (2) ° -r, 3 N0-R' LJ Π ΙΟ R'7v / —o / —o (3> XP —O A “D” - / V —0 - FT (4)

R'e'-O

q * - Jp 15

O-yy-O

R'-O-P Y V O R \ (5)

O— ”—O

20 R ', 4 (6) (?) / H ??'? r ° 'r'

25 \ r = B'S

o ^ Ty-R · .. I- ^ J2 · R14. y '30 in which the indices are integers and n' is 2, 3 or 4; p'1 or 2; q 'is 2 or 3; r 'is 4-12; y 'is 1, 2 or 3; and z 'is 1-6; A ', when n' is 2, C 2 -C 18 alkylene; C2 -C12 interrupted by oxygen, sulfur or —NR ’ή—; a group of the formula 1008373 22 R's, η *.

"φ ^ - · -0β-0 R'e is R, 6 or phenylene; 10 A ', if n' is 3, is a group of the formula -Cr.H2r» -i-; CH2— A ', if n 'is A, -CH 2 -C-CH 2 -; ch 2 -A "has the meaning of A' when n 'is 2; B 'is a direct bond, -CH2-, -CHR' /, -, -CR'jR '/ r, -, sulfur or C5 ~ C7 cycloalkylidene, or cyclohexylidene which is not in positions 3, 4 and / or 5 1-4 C 1 -C 18 alkyl groups are substituted; D ', when p' is 1, is methyl and when p 'is 2 -CH 2 OCH 2 -; E ', when y' is 1, C 1 -C 18 alkyl, -OR'i or halogen; E ', when y' is 2, -0-A is "-0-; E", when y 'is 3. A group of the formula ΡΡΡ0 (0Η20-) 3 or N (CH 2 CH 2 O) 3; Q'is the radical of an at least z'-worthy alcohol or phenol, this radical being attached to the phosphorus atom via the oxygen atom; R'n R'2 and R'3 are independently unsubstituted or with halogen, -C00R -C 1 -CN- or -CONR 1 'R' *, substituted C 1 -C 18 alkyl; C 2 -C 18 alkyl interrupted by oxygen, sulfur or -NR'4 -; C7-C9 phenyl-alkyl; C- -CJ 2 cycloalkyl, phenyl or naphthyl; naphthyl or phenyl substituted with halogen, 1-3 alkyl groups or alkoxy groups having a total of 1-18 carbon atoms or with C7-C9 phenylalkyl; or they are a group of the formula R5

"(CH ^ KÏf" 0H

* '· 40 1008373 23 where m' is an integer in the range 3 ~ 6; R'z, hydrogen, C 1 -C 18 alkyl, C 5 -C 12 cycloalkyl or C 7 -C 9 phenylalkyl, R 5 and R 6 are independently hydrogen, C 1 -C 6 alkyl or C 5 -C 6 cycloakyl, 5 R 7 and R'8, when q'2 is independently of one another C 1 -C *, alkyl or together are a 2,3-dehydropentamethylene group; and R'7 and R'g, when q'3 is 3, are methyl; R'n is hydrogen, C1 -C8 alkyl or cyclohexyl, R'15 is hydrogen or methyl and when two or more groups R'j /, and R'15 are present, these groups are identical or different, X 'and Y "each are a direct bond or oxygen, Z" is a direct bond, methylene, -C (R'16) 2- or sulfur, and R'16 is C1-C8 alkyl.

Of particular interest are compositions comprising as component (c) 15 a phosphite or phosphonite of the formula 1, 2, 5 or 6, wherein n 'is 2 and y' is 1, 2 or 3; A 'is C 2 -C 18 alkylene, p-phenylene or p-biphenylene, E', when y 'is 1, is C 1 -C 18 alkyl, -OR'j or fluoro; E ', when y' is 2, p-biphenylene, E ', when y' is 3, N is (CH 2 CH 2 O) 3; R'j, R'2 and R'3 independently of one another are C 1 -C 18 alkyl, C 7 -C 9 phenylalkyl, cyclohexyl, phenyl or phenyl substituted with 1-3 alkyl groups having a total of 1-18 carbon atoms; R 1 is hydrogen or C 1 -C 8 alkyl, R 1 15 is hydrogen or methyl; X 'is a direct bond, Y' is oxygen, Z 'is a direct bond or -CH (R' 16) - and R '16 is C 1 -C 6 alkyl.

Likewise of interest are compositions comprising as component (c) a phosphite or phosphonite of the formula 1, 2, 5 or 6, wherein n 'is 2 and y' is 1 or 3; A 'is p-biphenylene, 35 E', when y 'is 1, C 1 -C 18 is alkoxy or fluoro; E ", if y" is 3, N is (CH 2 CH 2 O-) 3; R'1 (R'2 and R'3 independently of one another are C 1 -C 18 alkyl or phenyl substituted with 2 or 3 alkyl groups having a total of 2-12 carbon atoms; R'n methyl or tert-butyl R 'is 5 hydrogen, X' is a direct bond, 5 Y 'is oxygen, and Z' is a direct bond, methylene or -CH (CH 3) -.

Particular preference is given to compositions comprising as component (c) a phosphite or phosphonite of the formula 1, 2 or 6.

Particular preference is given to compositions comprising as component (c) at least one component of the formula VII R2 -O- P (VII) R3 R4 LJ 3 wherein 20 R 1 and R 2 independently of each other are hydrogen, C 2 -C 8 alkyl, cyclohexyl or phenyl and R 3 and R 3 independently from each other are hydrogen or C 1 -C 18 alkyl.

The following compounds are examples of organic phosphites and phosphonites which are particularly suitable as component (c) in the new compositions.

Triphenylphosphite, diphenylalkylphosphites, phenyl dialkylphosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecylphosphite, di-stearylpentaerythritol diphospheryl, diphyl-phenyl-phenyl-phenyl-phosphyl (phospho-(Ir) phenyl) phospho-phosphite , Jj-di-tert-butylphenyl) pentaerythritol diphosphite (formula D), bis (2,6-di-tert-butyl - - - methylphenyl) pentaerythritol diphosphite (formula E), bis-isodecyloxypentaerythritol diphosphite, bis (2, il-di-tert -butyl-6-methyl-phenyl) pentaerythritol diphosphite, bis (2, k, 6-tri-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2, ^ - di-35 tert-butylphenyl) -k, k'- biphenylene diphosphonite (Irgafos® PEP-Q, Ciba-Geigy, Formula H), 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-di-benzo [d, g] -1.2 -dioxaphosphocine (formula C), 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo [d, g] -1,3,2-dioxaphosphocine (formula A), 1008373 bis ( 2, ^ - di-tert-butyl-6-methylphenylmethylphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethylphosphite (form ule G).

Particular preference is given to the use of the following phosphites and phosphonites: 5 tris (2,4-di-tert-butylphenyl) phosphite (Irgafo ^ D 168, Ciba-Geigy), tris- (nonylphenyl) phosphite, Γ (ch ^ c. ^ / c <ch3> 3

XP

(A) H, C — CH P — F J P-O-CHjCH, N (™

Pr0 Xï ° ^ Λο, οη3) 3 (ch3) 3c L J3 15 (εΗλεγτγ ° (ΟΗ3) 3 WAo TV — O CH2CH (C4H9) CH2CH3 (C) 20 XY ° (CH3) 3C- ^ N ^ \ C (CH3 ) 3 25 (D)

C (CH3) 3 (CH3) 3C

3 ° C (CH3) 3 <ch3) 3c (e,

C (CH3) 3 (CH3) 3C

35 1008373 26 ch3 - (F) H3C-C-CH3 ^ / 0_Λ / ~ ° \ Λ Jv. .o-p-och2ch3

5 H37C “0” P'0_X_o, P ° ^ H3 <\ XT

H3C CH3 l_ 3 - '2 10 (H)

C (CH3) 3 "j Γ TO

(CH ^ c - ^^> - p-- ° - {2 ^ - ° <0ΗΛ 15 L J2 L J2

Tris (2, ^ - di-tert-butylphenyl) phosphite [Irgafoö® 168, Ciba Spezia-litatencheroie AG], bls (2, ii-di-tert-butyl-6-nethylphenyl) ethylphosphite 20 [Irgafos® 38, Ciba Spezialite chemistry AG, formula (G)] or tetra-kis (2, - - di-tert-butylphenyl) -¾, 4'-biphenylene diphosphonite [Irgafo ^ S) PEP-Q, Ciba Spezialitatenchemie AG, formula (H)] have very special preference.

The above-mentioned organic phosphites and phosphonites are known compounds; many of them are commercially available.

Compositions of interest include those comprising as component (d) at least one compound of the formula VI Γ h3c 3 / CH3 30> = \ (V1> HO -X - R '- n 35 where

Rj is C 1 -C 18 alkyl, n is 1, 2, 3 or 4, 1008373 27

O O

II II

X is methylene, -CH2-CH2-C-Y- or -CH2-C-O-CH2-CH2-, Y is oxygen or -NH-; and 5 if η is 1, 0

II

X is -CH 2 -CH 2 -C-Y-, wherein Y is attached to R 2 and R 2 is C 1 -C 12 alkyl; and 10 if n is 2, 0

II

X is -CH 2 -CH 2 -C-Y- wherein Y is attached to R 2 and R 2 is C 2 -C 12 alkylene or C 1 -C 12 alkyl-15 interrupted by oxygen or sulfur; or, when Y is -NH-, R2 is additionally a direct bond; and if n is 3, 0

II

X is methylene or -CH 2 -C-O-CH 2 -CH 2 - wherein the ethylene group is attached to R 2 and 1008373 is 28 R 2 ° ΥΝΥ; and 5 Ο if η is L \, 0

10 II

X is -CH2-CH2-C-Y- where Y is attached to R2 and R2 is C1 -C10 alkane tetrayl.

Alkyl of up to 25 carbon atoms is a branched or unbranched group, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-15-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methyl hylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3 "tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1, 3-trimethylhexyl, 1,1,3,3 "tetramethyl-pentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3 * 3.5.5" 20 hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hepta -decyl, octadecyl, eicosyl or docosyl. A preferred definition of Rx is methyl and tert-butyl. A particularly preferred definition of R 2 is C 1 -C 20 alkyl, especially C 1 -C 20 alkyl, for example C 1 -C 20 alkyl. A particularly preferred definition of R 2 is C 8 -C 18 alkyl, especially C 1 -C 20 alkyl, for example C 18 alkyl.

C 2 -C 12 alkylene is a branched or unbranched group, for example ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene or dodecamethylene. A preferred definition of R2 is, for example, C2-C10 alkylene, especially C2-C10 alkylene. A particularly preferred definition of R 2 is, for example, C 1 -C 8 alkylene, especially C 1 -C 8 alkylene, for example hexamethylene.

C 4 -C 12 alkylene interrupted by oxygen or sulfur may be interrupted one or more times and is, for example, -CH2-0-CH2CH2-0-CH2-, 35 -CH2- {0-CH2CH2-) 20-CH2-, -CH2- ( O-CH2CH2-) -30-CH2-, -C1 -TO-CHjCHj-1 / .O-CHj-, -CH2CH2-O-CH2CH2-0-CH2CH2- or -CH2CH2-S-CH2CH2-. A preferred definition of R 2 is C 1 -C 10 alkylene, interrupted by oxygen or sulfur, C 1 -C 10 alkylene, in particular C 2 -C 8 alkylene interrupted by oxygen or sulfur, for example C 2 -C 8 alkyl, interrupted by oxygen or sulfur. A particularly preferred meaning of R 2 is -CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 2 - or -CH 2 CH 2 -S-CH 2 CH 2 -.

ch2-

, I

Alkane tetrayl of 4-10 carbon atoms is, for example, -CH2-C-CH2-CH2-

II II

(pentaerythrityl), -CH2-CH-CH-CH2-, -CH2-CH2-CH-CH-CH2-, 10

II II

-ch2-ch2-ch-ch-ch2-ch2-, -ch2 —CH2 -ch-ch2 —CH — CH2 —CH2 - or

I I

15 -CH2-CH2-CH-CH2-CH2-CH-CH2-CH2-. Pentaerythritol is preferred.

Component (d) may also include mixtures of various sterically hindered phenols of the formula VI.

Compositions of interest include those comprising as component (d) at least one compound of the formula VI, wherein - when η is 1 - R 2 is C 1 -C 20 alkyl.

Preference is given to compositions comprising as component (d) at least one compound of the formula VI, wherein when n is 2, R 2 is C 2 -C 8 alkylene or C 1 -C 8 alkylene interrupted by oxygen or sulfur; or, when Y is -NH-, R2 is additionally a direct bond; and when n is 4, R2 is C4-C8 alkane tetrayl.

Likewise, preference is given to compositions comprising as component (d) at least one compound of the formula VI, wherein

Rj is methyl or tert-butyl, η is 1, 2 or 4, 0

II

35 x is -CH2-CH2-C-Y-, Y is oxygen or -NH-; and when η is 1, R 2 is C 1 -C 18 alkyl; and when n is 2, 40 is R 2 alkylene or oxygen interrupted is C 1 -C 6 alkylene; and when n is 4, R 2 is C 1 -C 6 alkane tetrayl.

Likewise of interest are compositions comprising as 1008373 component (d) at least one compound of the formula VI, the compound of the formula VI being a compound of the formula V1 to V1h

H.C

5 / CH3

H3C1> = \ II

HO — U /) CH, - CH.— C — NH (CH2), - V y 2 2 2 3 (Vla), Irganox 1098 HX ^ / / ch3 10 H.C 3 L 3 J2

H.C

3 \ / CH3 15 HsclK_ ° 1 H0 — VV — CH2 ~ CH2 ~ C — 0 — C18H37 (Vlb), Irganox®1076 HX ^ / c \ / CH3 h3c 20 h3c \ / CH3 25 -> V_ "25 H0 ^^ _CH_CH_0_0_CHr-c (v | c) ilrgano, .1010 H3C-C ^ / ch3 HX 3 L 3 J4 30

HX

\ ^ CH.

H3C "\ fi HO— ^ CH - CH - C - O — CH2— CH2— O — CH2 - (Fld) 'lr9anox 245

H3C

L J2 - • m 1008373 31

H.C

\ / CH3

-> v. II

5 HO— (v /) CH2 — CH2— c — o— (CH), - 5 \ y 2. 2 2 3 (Vie), lrganox * 259 H3C- 'c \ / CH3 h3c 3 L 3 J 2 10

H.C

\ / CH3 v'y = \ δ

HO— (v /) CH2— CH2— C — O - (CH2) 2 S

15 Y__7 (Vlf), lrganoxs1035 H3C ^ / c \ / CH3 h3c 3 L 3 J 2

20 rH

R3 H3C / CH3

/ CN

ΟγΝ γΟ / = / CH3 dj f | jv R3 = CH2 ~~ Y Y — 0H (Vlg), lrganox * 3114 R3 Y R3 N \ ^ CH3

25 0 A

H3C CH3 R3 H3C / CH3 30 I, C \ || / = / CH3 μ m Ra = - (CH2) 2 -O-C-CH2- /, - OH (Vlh), Irganox® 3125.

y M ^ ch3 0 Μ3υ CH.

35 1008373 32 5 10 Irganox® 1098, Irganok® 1076, Irgano; ® 1010, Irgano® ® 245, Irga no: ® 259. Irgano> ® 3H4, Irganox® 1035 and Irgano; ® 3125 are protected trade names of Ciba Spezialitëtenchemie AG,

Preference is given to compositions comprising as component (d) at least one compound of the formula VI, wherein the compound of the formula VI is a compound of the formula V1a, VIb, VIc or VId, in particular a compound with the formula Vla, v VIb or VIc.

Component (d) of the new composition and the compounds of formula VI are known and in some cases commercially available. Possible preparation methods for the compounds of the formula VI can be found, for example, in U.S. Pat. Nos. 3330859 or 3960928.

Compositions of interest include those comprising, as component (e), at least one group of the formula XII or XIII (XII) CH, G, (XIII) G CH2 '^) -'G2 g ch, Q Lg ; -nJk G CH2 ^ | G - CHr3 j 30 ch3 ch3 where G is hydrogen or methyl and 35 Gj and G2 are hydrogen, methyl or together oxygen.

Of particular interest are compositions comprising as component (e) at least one compound from the group of the sterically hindered amines from the class of compounds described under (a ') to 1008373 33 and with (g'), which comprises at least a group of the formula XII or XIII.

(a ') Compounds of the formula Xlla 5 Γ CH3 G, G CH, —J / G “Vy 0 - G'» (Xlla) G - CH .- 'i CH3 J n 10 where n is a number of 1 -4, G and Gj are independently hydrogen or methyl,

Gu hydrogen, 0 ', hydroxyl, NO, -CH 2 CN, C 1 -C 18 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 1 -C 12 aralkyl, C 1 -C 8 alkoxy, C 5 -C 9 cycloalkoxy, C 1 -C 9

V

phenylalkoxy, C 1 -C 8 alkanoyl, C 3 -C 5 alkenoyl, C 1 -C 18 alkanoyloxy, benzyl oxy, glycidyl or a group -CH 2 CH {OH) -Z, wherein G 1 is preferably hydrogen, C 1 -C 18, alkyl, allyl, is benzyl, acetyl or acryloyl, Z is hydrogen, methyl or phenyl and when η is 1, G12 is hydrogen, C 1 -C 18 alkyl, which is continuous or interrupted by one or more oxygen atoms, or cyanoethyl, benzyl, glycidyl, a one -valent group of an aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus containing acid or a monovalent silyl group, preferably a group of an aliphatic carboxylic acid with 2-18 carbon atoms, of a cycloaliphatic carboxylic acid with 7-15 carbon atoms , of an α, β-unsaturated carboxylic acid of 3-5 carbon atoms or of an aromatic carboxylic acid of 7-15 carbon atoms, the carboxylic acid being substituted at least 1-3 times 30 with -C00Z12 in the aliphatic, cycloaliphatic or aromatic group Z] 2 are hydrogen, C 1 -C 20 al kyl, C 3 -C 12 alkenyl, C 5 -C 7 cycloalkyl or benzyl and when n is 2, 35 G 12 C 2 -C 12 alkylene, C 1 -C 12 alkenylene, xylylene, a divalent group of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid , dicarbamic acid or phosphorus-containing acid or a divalent silyl group, preferably a group of an aliphatic dicarboxylic acid 1008373 34 acid of 2-36 carbon atoms, of a cycloaliphatic or aromatic dicarboxylic acid of 8-14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid with 8 -14 carbon atoms, wherein the dicarboxylic acid can be substituted in any case with 1 or 2 groups -COOZ12 in the 5 aliphatic, cycloaliphatic or aromatic group, and when n is 3, G12 is a trivalent group of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid which may be substituted in the aliphatic, cycloaliphatic or aromatic group with -C00Z12, of an aromatic tricarbamic acid or of a phosphorus-containing acid, or a three-phase is a silyl group, and when n is 4, G12 is a tetravalent group of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

The indicated carboxylic acid groups include in any case groups of the formula {-C0) nR, the meaning of n being given above and the meaning of R being apparent from the stated definition, C 1 -C 12 alkyl substituents are, for example, methyl, ethyl, n-pro -20 pyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

As C 1 -C 18 alkyl, Gu or G 12 can be, for example, the groups shown above and also, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

When Gu is C3-C8 alkenyl, it may be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tert-butyl-2-butenyl.

Gn as C3-C8 alkynyl is preferably propargyl.

Gjj as Cy-C12 aralkyl is preferably phenethyl and especially benzyl.

Gn as C 1 -C 6 alkanoyl is, for example, formyl, propionyl, butyryl, octanoyl, but preferably acetyl and as C 3 -C 5 alkenoyl, in particular acryloyl.

G12 as a monovalent group of a carboxylic acid is, for example, a acetic acid, caproic acid, stearic acid, acrylic acid, methacrylic acid, benzoic acid or β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid group.

For example, if G12 is a monovalent silyl group, then it is a group of the formula - (C3H23) —Si (Z ') 2Z ", where j is an integer 1 008373 in the range of 2-5 and Z' and Z "are independently C 1 -C 18 alkyl or C 1 -C 18 alkoxy.

For example, if G12 is a divalent group of a dicarboxylic acid, it is, for example, a malonic, succinic, glutaric, adi-5 pineic, turmeric, sebacic, maleic, itaconic, phthalic, dibutylmalonic, dibenzylmalonic acid. -, butyl (3.5-Cl-tert-butyl-4-hydroxybenzyl) malonic or bicyclohepenedicarboxylic acid group.

If G12 is a trivalent group of a tricarboxylic acid, it is, for example, a trimellitic, citric or nitrilotriacetic acid group.

If Gj2 is a tetravalent group of a tetracarboxylic acid, it is, for example, the tetravalent group of butane-1,2,3-tetracarboxylic acid or of pyromellitic acid.

If G12 is a divalent group of a dicarbamic acid then it is, for example, a hexamethylenedicarbamic acid or a 2,4-tolylene dicarbamic acid group. v

Preference is given to compounds of the formula Xlla in which G is hydrogen, Gn is hydrogen or methyl, n is 2 and G, 2 is the diacyl group of an aliphatic dicarboxylic acid having 4-12 carbon atoms.

Examples of polyalkylpiperidine compounds of this class are the following compounds: 1) 4-hydroxy-2,2,6,6-tetramethylpiperidine 2) 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine 25 3) 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine 4) 1- (4-tert-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine 5) 4- stearoyloxy-2,2,6,6-tetramethylpiperidine 6) 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine 7) 4-methacryloyloxy-1,2,6,6,6-pentamethylpiperidine 30 8) 1,2,2,6,6-pentamethylpiperidin-4-yl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate 9) di (1-benzyl-2,2,6,6-tetramethylpiperidine) 4-yl) maleate 10) di (2,2,6,6-tetramethylpiperidin-4-yl) succinate 11) di (2,2,6,6-tetramethylpiperidin-4-yl) glutarate 12) di (2, 2,6,6-tetramethylpiperidin-4-yl) adipate 13) di (2,2,6,6-tetramethylpiperidin-4-yl) sebacate 14) di (1,2,2,6,6-pentamethylpiperidin-4- yl) sebacate 15) di (1,2,3,6-tetramethyl-2,6-diethylpiperidin-4-yl) sebacate 1008373 36 16) di (1-allyl-2,2,6,6-tetramethylpiperidin e-4-yl) phthalate 17) 1-hydroxy-4-p-cyanoethyloxy-2,2,6,6-tetramethylpiperidine 18) 1-acetyl-2,2,6,6-tetramethylpiperidin-4-ylacetate 19) tri (2,2,6,6-tetramethylpiperidin-4-yl) trimellietate 20) 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidin 21) di (2,2,6,6-tetramethylpiperidin- 4-yl) diethyl malonate 22) di (1,2,6,6,6-pentamethylpiperidin-4-yl) dibutyl malonate 23) di (1,2,2,6,6-pentaroethylpiperidin-4-yl) butyl (3.5 ~ di-tert-butyl-4-hydroxybenzyl) malonate 10 24) di (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate 25) di (1-cyclohexyloxy-2,2,6,6 -tetramethylpiperidin-4-yl) sebacate 26) hexane-1 ', 6' bis (4-carbamoyloxy-1-butyl-2,2,6,6-tetramethyl-piperidine) 27) toluene-2 ', 4'- bis (4-carbamoyloxy-1-propyl-2,2,6,6-tetramethyl-15-piperidine) 28) dimethyl bis (2,2,6,6-tetramethylpiperidine-4-oxy) silane

V

29) phenyltris (2,2,6,6-tetramethylpiperidin-4-oxy) silane 30) tris (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite 31) tris (1-propyl-) 2,2,6,6-tetramethylpiperidin-4-yl) phosphate 32) phenyl [bis (1,2,2,6,6-pentamethylpiperidin-4-yl)] phosphonate 33) 4-hydroxy-1,2, 2,6,6-pentamethylpiperidine 34) 4-hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidine 35) 4-hydroxy-N- (2-hydroxypropyl) -2,2,6,6-tetramethylpiperidine 36 1-glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine.

(B ') Compounds of formula Xllb

CH3 G

G CH2 - y / Gi3 N G '(xnb) 30 G - CH, ^ | CH,. L 3 -1 n where n is the number 1 or 2, 35 G, Gj and Gn are as defined at (a '), G13 hydrogen, C 1 -C 6 alkyl, C 2 -C 5 hydroxyalkyl, C 5 -C 7 cycloalkyl, C 7 -C8 aralkyl, C2-Cl8 alkanoyl, C3-C5 alkenoyl, benzoyl or a group of the formula 1008373 37 CH, rg ~ ch2 ^ _V '5 G-CHf \ CH3 and when η is 1, 10 Gn hydrogen, Ci ~ C 1-8 alkyl, C 3 -C 8 alkenyl, C 5 -C 7 cycloalkyl or C 1 -C 6 alkyl substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide group; glycidyl, a group of the formula -CH 2 -CH (OH) -Z or of the formula -C0NH-Z, where Z is hydrogen, methyl or phenyl, and when n is 2, 1? Gli (C2-C12alkylene, C6-C12 arylene, xylylene, a group -CH2-CH (0H) -CH2- or a group -CH2-CH (0H) -CH2-0-D-0-, where D is C2 -C10 alkylene, C6-C15 arylene, C6-CJ2 cycloalkylene, or provided G13 is not alkanoyl, alkenoyl or benzoyl, G ^ additionally 1-oxo-C2-C2 alkylene, a divalent group of one aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or else the group -CO-, or when η is 1, G13 and Gj4 together may be the divalent group of a laiphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

C 1 -C 12 or C 1 -C 12 alkyl substituents have the meanings already defined in (a ').

C5-C7 cycloalkyl substituents are especially cyclohexyl.

Gj3 as C7-C8 aralkyl is in particular phenylethyl or especially benzyl. As C2-C3 hydroxyalkyl, GJ3 is in particular 2-hydroxyethyl or 2-hydroxypropyl.

G13 as C 2 -C 18 alkanoyl is, for example, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl and as C 3 -C 5 alkenoyl especially acryloyl.

When G 1, C 2 -C 8 is alkenoyl, it is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

Gii as C 1 -C 1 alkyl substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide group may include, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2- (dimethylaminocarbonyl) ethyl.

1008373 38 C2-C12alkylene substituents are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

C6-C15 arylene substituents are, for example, o-, m- or p-5 phenylene, 1,4-naphthylene or 4,4'-diphenylene.

Cyclohexylene should particularly be mentioned as C-C12 cycloalkylene.

Preference is given to compounds of the formula Ib wherein η is 1 or 2, Gu is hydrogen or methyl, G13 is hydrogen, C 1 -C 10 alkyl, or a group of the formula ch 3 g G-15 e-CH 2 r is ch 3 * and G 1 is when n = 1 is hydrogen or C 1 -C 12 alkyl and, when n = 2, is C 2 -C 8 alkylene or 1-oxo-C 2 -C 8 alkylene.

Examples of polyalkylpiperidine compounds of this class are the following compounds: 37) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1,6-diamine 38) N, N ' bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1,6-diacetamide 39) bis (2,2,6,6-tetramethylpiperidin-4-yl) amine 40) 4-benzoylamino-2 2,6,6-tetramethylpiperidine 41) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-dibutyl adipamide (42) N.N'-bis (2, 2,6,6-tetramethylpiperidin-4-yl) -N, N'-dicyclohexyl-2-hydroxypropylene-1,3-diamine 43) N, N'-bis (2,2,6,6-tetramethylpiperidin-4- yl) -p-xylylendiamine 44) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) succinamide 45) di (2,2,6,6-tetramethylpiperidin-4-yl) -N - (2,2,6,6-tetramethyl-35-piperidin-4-yl) -p-aminodipropionate 46) the compound of the formula 1008373 39 CH3

H3C ^ -1 OH

5 h3c-nV-n-ch-ch-ch2-o-c H3C I 'CH3 ch3 L 3 -J 2 10 47) (bis-2-hydroxyethylamino) -1,2,2,6,6-pentamethylpiperidine 48 ) 4- (3-methyl-4-hydroxy-5-tert-butylbenzamido) -2,2,6,6-tetraraethyl-piperidine 49) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine.

(c ') Compounds of the formula XIIc 15 CHa r G-CH2-4- /' G “Ny_X ^ G“ <x "c> G - CHf \ ° 20 CH3 LJ n where n is the number 1 or 2, G , and Gu have the meanings defined in (a ') and 25 when η is 1, G] 5 is C2-C8 alkylene or C2-C8 hydroxyalkylene or CA-C22 acyloxyalkylene and when n is 2, G15 is the group (-CH2) 2C (CH2-) 2.

When G15 is C2-C8 alkylene or C2-C8 hydroxyalkylene, it is, for example, ethylene, 1-methyl ethylene, propylene, 2-ethyl propylene or 2-ethyl-2-hydroxymethyl propylene.

For example, G 5 as C 1 -C 22 acyloxyalkylene is 2-ethyl-2-acetoxy-methylpropylene.

Examples of class polyalkylpiperidine compounds are the following: 50) 9-aza-8,8,10,10-tetramethyl-1,5 ”dioxaspiro [5.5] undecane 51) 9-aza-8,8,10 10-tetramethyl-3-ethyl-1,5-dioxaspiro [5.5] undecane 1008373 40 52) 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro [4.5] decane 53) 9-aza-3-hydroxymethyl -3-ethyl-8,8,9,10,10-pentaniethyl-lt5-dioxa-spiro [5 · 5] un <3ecane 54) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10, 10-tetramethyl-1,5-5 diOxaspiro [5-5] undecane 55) 2,2,6,6-tetramethylpiperidine-4-spiro-2 '- (1', 3'dioxane) -5'-spiro-5 "- (1", 3 "" dioxane) -2 "-spiro-4" '- (2,2 ", 6", 6 "- tetramethylpiperidin).

<d ') Compounds of the formulas Xlld, Xlle and Xllf, with 10 compounds of the formula XIIf being preferred ch3 r 9 * G-CH2-Jpy' N-C * 15 GN) <I (X'M) \ -J Xc — N - S „

G — ΟΗζ \ II

CH3 O

LJ n 20 j CH3 q 1 G CH2—1 —— / 1 o — C · ^ 2 g- \ X i {XI, e) G-CHr ^ l ï c * 0 nr. CH3 H u 25 3 ch3 r T1 30 0_c-t G- vJSs-i - e „<xm>

G — CH 2 I II

ch3 o L J n 35 where n is the number 1 or 2, G, Gj and Gn are as defined in (a '), 1008373 m

Gle is hydrogen, C 1 -C 12 alkyl, allyl, benzyl, glycidyl, or C 2 -C 6 alkoxy alkyl, and if η is 1, G17 is hydrogen, C 1 -C 12 alkyl, C3-C5 alkenyl, C7-C9 aralkyl, C5 ~ C7 cyclo- Alkyl, C2-C19, hydroxyalkyl, C2-C6 alkoxyalkyl, C6-C10 aryl, glycidyl or a group of the formula - (CH2) p-C00-Q or of the formula - (CH2) p-0-C0-Q where p is 1 or 2 and Q is C 1 -C * alkyl or phenyl, and when n is 2, G 1? C 2 -C 12 alkylene, C 1 -C 12 alkenylene, C 6 -C 12 arylene, a group 10 -CH 2 -CH (0H) -CH 2 -O-D-0-CH 2 -CH (0H) -CH 2 - where D is C2- C10 alkylene, C6-C15 arylene, C6-C12 cycloalkylene or a group -CH2CH (OZ ') CH2- (0CH2-CH (OZ') CH2) 2, wherein Z 'is hydrogen, C 1 -C 18 alkyl, allyl, benzyl C2-C12 is alkanoyl or benzoyl,

Tj and T2 are independently hydrogen, C 1 -C 12 alkyl or unsubstituted or halogen or C 1 -C 18 alkyl substituted C6-C10 aryl or C7-C9 aralkyl or Tj and T2, together with the carbon atom to which they are genes, to form a C5-Cli (cycloalkane ring.

C 1 -C 12 alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, 20 n-nonyl, n-decyl, n undecyl or n-dodecyl.

Substituents in the sense of C 1 -C 18 alkyl can be, for example, the groups mentioned above and also, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

C2-C6 alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.

If G, 7 is C -) - C5 alkenyl, it is, for example, 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.

G, 7, Tj and T2 as C7-C9 aralkyl are in particular phenethyl or especially benzyl. When Tj and T2 form a cycloalkane ring together with the carbon atom, this may be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.

For example, if G17 is C 2 -C 3, hydroxyalkyl, then it is 2-hydroxy-35 ethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

G17, Tj and T2 as C6 -C10 aryl are in particular phenyl, α- or β-naphthyl, which are unsubstituted or substituted with halogen or C1 -C4 alkyl.

1008373 42

When G17 is C 2 -C 12 alkylene, it is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

G17 as Cu-C12 alkenylene is in particular 2-butenylene, 2-5 pentenylene or 3 "hexenylene.

Like G1? C6-C12 is arylene, for example it is o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

If Z 'is C 2 -C 12 alkanoyl, it is, for example, propionyl, butyryl, octanoyl, dodecanoyl, but preferably acetyl.

10 D is as C 2 -C 10 alkylene, C 12 -C 18 arylene or C 6 -C 12 cycloalkylene as defined in (b ').

Examples of class polyalkylpiperidine compounds are the following: 56) 3-benzyl-1,3,8-triaza-7.7.9.9-tetramethylspiro [4.5] decane-2,4-dione 15 57) 3-n-octyl -1,3.8-triaza-7.7.9.9 "tetramethylspiro [4.5] decane-2,4-dione> 58) 3-allyl-1,3,8-triaza-1, 7,7,9.9-pentamethylspiro [4.5] decane-2 1,4-dione 59) 3-glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro [4.5] decane-2,4-20 dione 60) 1,3,7,7,8,9,9- heptamethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione 61) 2-isopropyl-7,7.9.9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro [4.5] - decane 62) 2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro [4.5] -25 decane 63) 2,2,4,4-tetramethyl-7-oxa- 3,20-diaza-21-oxodispiro [5.1.11.2] heneic cosane 64) 2-butyl-7.7.9,9 ”tetramethyl-1-oxa-4,8-diaza-3-oxospiro [4.5] decane and at preferred 65) 8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9 "tetramethylspiro [4,5] decane-2,4-dione or the compounds of the following formulas: 1008373 43 CH . V o

66) Η, Λ I ° H

5 \ 'C N - CH2 - CH - CH - O - CH, CH - OH

h3c "1 ii CH3 o L J2

10 CH3 VO

H3C ^ y N — Z

67) H3C-N V I

\ 'C-N - CH? - CH-— CH2--

h3cH II

CH3 O

15 L J 2 v ch3 o

H3C2) - N - Z

68) H - N I / = \ h3c ^ _ / ir N <L_J) CH2 ch3 o L J 2 25 - (CH2) 9 CH3 H2C. \ h3c ^ _1 0_ ^ ch2

69) 7 I

IN —IN Y I

\ f c N CH2CH2COOC12H25, n H.C'T || 30 ch3 ο (e ') Compounds of formula Xllg, which in turn are preferred 358373 Μ Γ Gig 1

X

Ν ^ Ν / γη_ν Λ J — ο. (Χ "9) 5 0, ΓΝ J η where η is the number 1 or 2 and Gl8 is a group with one of the following formulas ch3 Gi CH3G, G-CH ^ j / <3-0Η2Ο_ ^ 02 G -nV- (A) —E— or GN N - (A) - E— * 5 G - CHr ^ 1 G — CHfi CH3 ch3 where G and Gn are as defined in (a '),

Gj and G2 are hydrogen, methyl or together a substituent = 0, 20 is E -0- or —NG13 ~, A is C2-C6 alkylene or - (CH2) 3-0-, x is the number 0 or 1, G13 hydrogen, 0: -0] 2 alkyl, C 2 -C 5 hydroxyalkyl or C 5 -C 7 cycloalkyl, G 1 (j is the same as G 1 8 or one of the groups -NG21G22, -0G23, -NHCH20G23 or -N (CH20G23) 2 , G20, if n = 1, is the same as G18 or G19 and, if n = 2, G20 is a group -EBE-, where B is C2-C8alkylene or by 1 or 2 groups -N (G21) -interrupted C2- C8 is alkylene, G21 is C 1 -C 12 alkyl, cyclohexyl, benzyl or C 1 -C 3, hydroxyalkyl or a group of the formula

CH3 G

G — CH2 ^ _ / 1

GiTNx y— G — CHfi 35 CH3 or a group of the formula 1 008373 Ί5 ch3 I CH3 h3C ^) _ n ^ n L-CH3 5 \ -C ° ”5 H3C \ I n-C4H9 n-C4H9 [^ CH3 OH3 CHg is 10 G22 C 1 -C 12 alkyl, cyclohexyl, benzyl or C 1 -C 16 hydroxyalkyl, or G21 and G22 together are C / -C 5 alkylene or C 1 -C 8 oxalkylene, for example -CH 2 CH 2 OCH 2 CH 2 -, or a group of the formula -CH 2 CH 2 N (Gn) CH 2 CH 2 - and G 23 is hydrogen, C 1 -C 12 alkyl or phenyl.

C 1 -C 2 alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n- decyl, n-undecyl or n-dodecyl. For example, C 2 -C 5 hydroxyalkyl substituents are 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

When A is C 2 -C 12 alkylene, it is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.

When G21 and G22 together are C1-C-alkylene or oxalkylene, this is, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.

Examples of polyalkylpiperidine compounds of this class are those having the following formulas: 25 CHa N (CH2CH3) 2

h3c ^ P n ^ N

7 °) H3C- N N-UN β-N (CH2CH3) 2 H3C Λ n-C4H9 30 ch3 CH3 N (H "C4h9) 2 cH3 H3C '^ - 1 N / N --L-" CH3 71) CH3CH— N yN - N - \ __ / N CH2CH3 C2H5 C2H5 N | ^ CH3 CH3 1 008373 46 CH, Ατ ^ (CH2) 3-0— ^ n-ch3 CH3 Hf | JN f ^ CH, 5 72) h = c - ^ A n ^ n ch = H3C-N) 0- (CH2) 3-N 1¾. 9H3 ^ a N rH Ach ‘ch3 (ch2) 3 — o— (n-ch3 10 I ch3 ch3“. A0 "·

CH - CH2 - (N-H

CH3 H | H ^ H3 73) Η3 ° '^) _ Λ N ^ ISI CHa 20 Η - N> -CH. — CH. N U- 9H3 Λ— 'I N N-H J ^ CHa h3c "1 H I / \

CH3 CH — CH2— (N-H

Tch3 ch3 25 30 35 1008373 47 rnhch2ch2 ^ ^ ch2ch2nhr ch3 V CH3 H3C- ^ 1_ N ^ N J ^ CH3

74) H - N y - N - N - ^ V-H

H3CJ ~ n'C4H9 n'C4H9 'I * CHj OH3 CH3 10 CH3 I ch3 H3C - ^ - λ N ^ N J ^ CH3

R = Η —N \ N-YY-N- (N-H

h3C ^ T 'n -C4H9 n -C4H9 | ^ CH3

CH3 PH

15 CHa

V

R R

I I

75) R-NH- (CH2) 3-N- (CH2) 2-N- (CH2) 3-NH-R

R has the same meaning as at compound 74.

R 'R'

I I

76) R '-NH- (CH2) 3-N- (CH2) 2 -N- (CH2) 3-NH-R' 25 CH 1 CH3 h3c ^ _L n <^ n / -VCH3 R. = H3C-n ) —N ^ Njl — N - <^ N-CHa 30 H3C "| n * C4H9 n-C4H9 pCH3 CH3 CH3 CH, R 'R' CH,

I I I I

77) r'-n- (ch2) 3-n- (CH2) 2-n- (ch2) 3-n-r 'R' has the same meaning as in compound 76.

1008373 i \ 8 HN-CH, -CH, -CH, -ch3 I>, H; iC 7 N ^ N, -L ^ CH3

5 H - ^ N N- ^ ^ N — H

n '^ 8 ^ 17 n' ^ 8 ^ 17 'I ^ CH, L CHa ch3 J2 10 ch2ch2oh • VO ^ CH, h3C-T T "ch3 15 79) N — n-C4H9 ch3 I ch3 H3C" ^ - χ N ^ \ l / ~ VCH3

HOCH2CH - N y-N-WNJJ-N- ^ N-CH2CH2OH

H3C n * C4H9 n "C4H9 N | xH3 20 CHa CH3 ch2-ch = ch2 H3CN ^^ CH3 25 h3c-Y Y ^ h, 80) N — n-C4H9 ch3 I ch3 N ^ N / —VCH3 30 H2C = CH —CH - N yN -NN-CH — CH = CH2 H3C ^ T ~ n-C4H9 n-C4H9 '^ CH3 CH3 CH3 35 (f) Oligomeric compounds or polymers whose repeating structural unit has a 2,2,6,6 tetraalkylpiperidine group contains, in particular polyesters, polyethers, polyamides, polyamines, polyethanes, polyurea, polyaminotriazines, poly (meth) acrylates, poly (meth) acrylamides and copolymers thereof comprising such groups.

Examples of 2,2,6,6-polyalkylpiperidine compounds of this class are those of the following formulas, where m is a number from 2 to about 200.

CH3 io _Uch3 o o

81 II

81) --o (N — CH2-CH — O — C — CH —CH-C-- j ^ CH3 CHa J J m 15 _ v CH3 UCH3 O o

82i \ II

--o- (N —CH2-CH — o — C— (CH2) —c-- 20 '| ^ H3 CH, J m CH3 25 L.ch2ch3 0 0 83) --NH— / N - CHj-CHj - CH - NH-0—1 ^> | —C-- h / TCH * ch3 ^ CH.

-I m 30 1008373 50 CH, / -; μ I 3 \ 3 HN - C-CH2— C-CH3 II 2 I 3 1 X CH3 ch3

5 N ^ N

--W Ji-N- (CH2) 6-N--

84) N I 26 I

H_C — I LCH3 H3cJ LcH3 H c'N "cH / N '" Yh

Hac 1 CH 3 I CH 3

10 Η H

m ~ OH ~

1, I.

* 5 N — CH - CH — CH2 - Λ 'h3c y ch3 20 H m

CH ^ CH

^ VCHa Η3 ° ^ - \ ίι "'ΐ4" 9 ίί 25 86) - ο- (Ν — CH2-CH = CH-CH — Ν) —Ο —C — CC-- r ~ CH3 η c ^ -7 ni.H, CH3 υ3υ ch3 J m 30 1008373 51 j ch3

N ^ N

87) - W Ji-N- (CH2) 6-N--

N j 6 I

10 H3cJ JUCH3 H3cJ "LcH3

H C ^ N "cH

H 3 C 1 CH; J H, C 1 CH 3

Η H

L J m 15 86) 9H 3 CH 3

LCH3 H3CsT Ο O

_r \ _ r \ _ II II

--O (N - CHj - \\ n — CH — N) —O — C— (CH2) —C-- ch3 3 H3C ch3 -1 m 25 r -.

CH3 1 / ch3 O C h5 o

89¾ / II II

öa '--O (N —CH2-CH2 — o-c — C-C--

H-ch, U

CH.

30 3 J m 1008373 52 Γ CH, Ί I 3 --CH C--

2 I

A*

o o

5 90)

HiC ~ K ^ cH3 h3c γ ch3 CH3 j _j m 10 Γ ch, η I 3 --CH — C--

C.H., <L

- .A

"• '> Ά0Η · h3c f ch3 CH3 J —1 m 20' 0

25 N ^ N

92) I II

- ^ - N- (ch2) 6-N--

N I 26 I

Hac-X JrCH3 h * caL Jr-CH3 up / N xru / n \ ^ l1 30 3 I 3 H, CI un3 Η Η * - - * m 35 1008373 53 --N- (CH2) 6-N- (CH2 ) 2-- 5 93> HjCJ ^ CH3 H »c I CH> η / I ch3

H 3 H

m 10 r 1

O O

II II

--N- (CH2) 6-N — C — CH-C-- 9} H3C "X JcCH3 H3C ^ C J ^ CH3 15 H3C Ï CH3 H3C ï CH3 L, H H J m

R R

20 I I

95) --N - (CH2) 2— N - (CH2) 2-- L -J m "where R is a group of the formula 25 ch3 I ch3 H3C '^) - L N ^ N --L-CH3

HjC n'C <H> η '° Λ T ^ CH3 30 ch3 CH3 or a branched chain

R

35 I

- (CH2) 2 —N-- _ __ π m 1 008373 54 and m 'and m "are each an integer in the range 0-200, with the proviso that m' + m" = m.

Further examples of polymers are reaction products of compounds of the formula CH3 HjC '-' f · * »h3c ~ J - o - c - ch2 H ~ 0 <1

10 h3c-v rNH

10 CH 3 O

with epichlorohydrin; polyesters of butane-1,2,3t4-tetracarboxylic acid with a bifunctional alcohol of the formula 15 CH 3 n o CH,

I I

HOCHl-C-CH X CH-C-CH 2 OH

1 O- / V 1, 1 ch 3 u 0 ch 3, of which the carboxyl side chains derived from the tetracarboxylic acid are esterified with 2,2,6,6-tetramethyl-4-hydroxypiperidine; compounds of the formula 25 Γ CH3 Ί --CH2— C - CH, - CH--

I I

CO, CH, CO, R

L 2 3 2 30 in which about a third of the groups R are -C 2 H 5 and the other groups 1008 373 55 CH,

Lcn,

- ~ \ N-H

* -> CHS

ch3 are 10 and m is a number in the range 2-200; or copolymers of which the repeating unit consists of two units, _k CH, 15 <Q> -C = ch3 and in any case a unit 20 ^ 13 ^ 27 and a unit 25 V-X JUch3 SO / N \ J h3c ^ ch3

H

(g ') Compounds of the formula XlIIa 1008373 56 CH3 η ". g-ch2 ^ _ ^ S — N N - G" (Xllla)

5 Q-CH 2

CH, L 3 J n 10 where n is the number 1 or 2 and where G and Gn are as defined at (a ') and G ^ is as defined at (b'), where GlZl is not the meanings -C0NH-Z and -CH2-CH (OH) -CH2-O-D-O-. Examples of such compounds are: CH3 CH, 15 H; c ^ {

100) H - N N-CH2-CH2-N N-H

h3c-V ^ ch3 O ch3 20 CH, ~ CH, h3c - ^ _! ^ ^ tCH3 101) H, C — NN —CHj — CHj — NN — CH, h3c ^ 0H ^ chs 25 ch3 0 ch3 CH3 n H3CO_> 102) H3C N N-CH - <fj> H3C ^ ch3 35 Of particular interest are compositions comprising as component (e) at least one compound of the formula H1, H2, H3. H4, H5, H6 and H7 include 1008373 57 ch3 ch3 H3C \ J 0 0 1 CH3 (H1) Tinuvin®123

\ II II f ~ K

H, 7CeO-NJO-C (CH2) -C-O ^ N-OC ^ 5. H3C ^ r TCH3 CH3 CH3 CH, (ch3) 3C o \ (H2) Tinuvin * 144 io _ / = \ I ii r ~ \ HO-U A CH — C - c — O (N — CH3

(CH ^ C

1 3 J 2 15 Hr? H3 9H3 (I (3) Tinuvin * 292 • S-Λ ï Ï _A ™> h3c-n Voc— (CH2) 8-co— (N-CH3 H3C ^ f-CH, CH3 CH3 20 CH3 "(H4) Tinuvin®622

1 / CH 3 O O

/ \ 11 II

--0 (N —CH2-CH —o — C — CH-CH-C-- f ^ CH3 25 CH3 3 J m CH, Iμ I | M3 (H5) Chimassorb 944 HN — C-CH -— c-CH II 2 I 3 30 X CH 3 ch 3

NK N

--W y-N- (CH2) 6-N-- ’Λ Λ H3C ^ JcCH3 H3C-1> CH3 35 H3C ΐ CH3 H3C 1Ϊ CH3

H 3 H

L - * m 1 008 373 5 58 (H6) Chimassorbe119, R 'R'

I I

R'- NH - (CH2) 3- N - (CH2) —N— (CH2) 3— NH - R 'CH3 I CH3 10 R' = H3C_Nv) —N — WNjL - N - ^ \ - ch3 H3C- T ~ n-C4H9 n-C4H9 f ^ CH3 CH3 CH3

HN-CH-CH.OH

15 X.

N ^ N

n-C4H9-N - N-n-C4H9 h3csC XrCH3 H * C "X JrCH3 20 H3C ^ CH3 H3C N CH3 (H7) o o 0 o 25 30 wherein m is a number in the range 2-200.

Component (e) of the new composition or the compounds of the sterically hindered amines type are known and some are commercially available.

Tinuvir® 123, Tinuviri®144, Tinuvir® 292, Tinuvir® 622, Chimas-1 008373 59 sorb® 9 ^ 4 and Chimassorb® 119 are protected trade names of Ciba Spezialitëtenchemie AG.

As component (e) of the new composition, those sterically hindered amines with a molecular weight of 5 or average molecular weight Mn in the range of 500-10,000, in particular in the range of 1000-10,000, are particularly preferably added. Of these, particular emphasis should be placed on those sterically hindered amines, which have a molecular weight or average molecular weight Mn in the range from 1500 to 10,000, for example in the range from 2000 to 7500.

Particular emphasis should be placed on those new compositions comprising as component (e) two or more compounds of the sterically hindered amines type.

The mixture of components (b), (c), (d) and (e) is suitable for stabilizing organic materials against oxidative, thermal or light-induced degradation. Examples of such materials are: 1. Polymers of mono- and diolefins, for example polypropylene, polyisobutylene, polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene, as well as polymers of cycloalkenes, such as, for example, of cyclopentene or norbornene, polyethylene (which may optionally be cross-linked), for example high density polyethylene (HDPE), high density polyethylene, high molecular weight (HDPE-HMW), high density polyethylene and ultra high molecular weight (HDPE-25 UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, ie the polymers of monoolefins shown in the previous paragraph, in particular polyethylene and poly-propylene, can be prepared by various, and in particular the following, processes: a) radical polymerization (usually under high pressure and at elevated temperature).

b) catalytic polymerization, in which the catalyst usually contains one or more metals from groups IVb, Vb, VIb or VIII of the

Periodic Table contains. These metals usually have one or more ligands, such as oxides, halides, alcoholates, esters, ethers, amines, alkyl groups, alkenyl groups and / or aryl groups, which may have either a π or a σ coordination. These metal complexes can be in the free form or they can be fixed on supports, such as, for example, on activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon oxide.

These catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be active as such in the polymerization or further activating agents can be used, such as, for example, metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyl oxanes, these metal elements being of groups Ia,

Ila and / or lilac of the Periodic Table. The activating agents can, for example, be modified with further ester, ether, amine or silyl ether groups. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (-15 Natta), TNZ (DuPont), Metallocene, or Single-Site (SSC) catalysts.

v 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 mono- and diolefins with each other or with other vinyl monomers, such as, for example, ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / butene-1 copolymers , Propylene / isobutylene copolymers, ethylene / butene-1 copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymer, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers and their copolymers with carbon monoxide 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; further mixtures of such copolymers with each other and with polymers mentioned under 1), for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers ( EAA), LLDPE / EVA, LLDPE / EAA and alternating or statistically constructed polyolefin / carbon monoxide copolymers and mixtures thereof with other polymers, such as, for example, polyamides.

Hydrocarbon resins (e.g. C5-C9), including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyolefins and starch.

5 5 · Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, such as, for example, styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate and methacrylate, styrene / maleic anhydride, styrene / acrylo-10 nitrile / raethyl acrylate; high impact blends of styrene copolymers and another polymer such as, for example, a polyacrylate, a diene polymer or an ethylene / propylene / diene terpolymer; and block copolymers of styrene, such as, for example, styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butene / styrene or styrene / ethylene / propylene / styrene.

Graft copolymers of -styrene or α-methylstyrene, such as, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl-20 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 resp. alkyl 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 mentioned under 6), which are for example known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers, such as, for example, polychloropene, chlorinated rubbers, the chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, in particular, polymers of halogen-containing vinyl compounds, such as, 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 chloride, or vinyl acetate copolymers.

1008373 62 9. Polymers derived from α, β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, modified with butyl acrylate, impact resistant.

10. Copolymerizing the monomers mentioned under 9) with each other or with other unsaturated monomers, such as, for example, acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate copolymers, acrylonitrile / vinyl halide copolymers or acrylonitrile / alkyl-10 methacrylate / butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; 15 as well as its copolymerization with the olefins mentioned under 1).

12. Homo- and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene 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 25 oxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters and polybutadienes, on the one hand, and aliphatic or aromatic polyisocyanates, on the other, and their precursors.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from amino carboxylic acids or the corresponding lactams, such as polyamide-4, polyamide-6, polyamide-6/6, -6/10, -6/9, -6/12, -4/6. -12/12, polyamide-11, polyaraide-12, aromatic polyamides starting from m-xylene, diamine and adipic acid; polyamides prepared from hexamethylenediamine and iso- and / or terephthalic acid and optionally an elastomer as a 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 1008373 grafted elastomers; or with polyethers, such as e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EP DM or ABS; as well as condensed polyamides ("RIM polyamide systems") during processing.

5 17 · Polyurea, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylol-10 cyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from polyethers with hydroxyl end groups; further polyesters modified with polycarbonates or MBS.

19 · Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Cross-linked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other, such as phenol / formaldehyde, urea / formaldehyde 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 cross-linking agents, as well as their low-flammability halogen-containing modifications.

2l4. Cross-linkable acrylic resins derived from substituted acrylates, such as, for example, from epoxy acrylates, urethane acrylates or polyester acrylates.

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

26. Cross-linked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example, products of diglycidyl ethers of bisphenol-A and bis-phenol-F, which are cross-linked with conventional curing agents, such as, for example, anhydrides or amines, with or without accelerators .

27. Natural polymers, such as cellulose, natural rubber, gelatin and chemically modified homologous derivatives thereof, such as cellulose acetates, cellulose propionates and cellulose butyrates, respectively. the cellulose ethers, such as methyl cellulose; as well as natural resins and their derivatives.

1008373 64 28. Blends (polyblends) of the aforementioned polymers, such as, for example, PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTB / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylics, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylic, 5 POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

29. Natural and synthetic organic materials, which are pure monomeric compounds or mixtures of such compounds, for example petroleum, animal and vegetable fats, oils and waxes, or oils, waxes and fats based on synthetic esters (eg phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with petroleum in any weight ratio commonly used as spinning compositions, as well as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubbers, such as e.g. natural rubber latex or latices of carboxylated styrene / butadiene copolymers.

The mixture of components (b), (c), (d) and (e) is also used for the production of polyurethane, in particular for the preparation of flexible polyurethane foams. In this context, the new compositions and the products produced from them are effectively protected against degradation. In particular, scorching during foam production is avoided.

The polyurethanes are obtained, for example, by reacting hydroxyl end groups containing polyethers, polyesters and polybutadienes with aliphatic or aromatic polyisocyanates.

Hydroxyl-terminated polyethers are known and are prepared, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, or epichlorohydrin with themselves, for example, in the presence of BF3, or by an addition reaction of these epoxides alone or as a mixture or sequentially, with starting components containing reactive hydrogen atoms, such as water, alcohols, aramoia or amines, e.g. ethylene glycol, propylene-1,3- and 1,2-glycol, trimethylol-35 propane, k, b'- dihydroxydiphenylpropane, aniline, ethanolamine or ethylenediamine. Sucrose polyethers are also suitable according to the invention. In many cases, preference is given to those polyethers which contain substantially (up to 90% by weight, based on all OH groups 1008373 65 contained in the polyether) primary OH groups. Polyethers modified with vinyl polymers, which are formed, for example, by the polymerization of styrene and acrylonitrile in the presence of polyethers, are also suitable, as well as polybutadienes containing OH groups.

These compounds generally have a molecular weight of 400-10,000 and are polyhydroxy compounds, in particular compounds containing two to eight hydroxyl groups, especially those with a molecular weight of 800 to 10,000, preferably 1000 to 6000, e.g. polyethers containing at least 2, generally 2-8, but preferably 2-4 hydroxyl groups, which are known per se for the preparation of homogeneous polyurethanes and cellular polyurethanes.

It is, of course, possible to use mixtures of the above compounds, which contain at least two isocyanate-reacting hydrogen atoms, and in particular have a molecular weight of 400-10,000.

Suitable polyisocyanates are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, eg ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecanediisocyanate, cyclobutane, 1,3-diisocyanate 3- and 1,4-diisocyanate and any desired mixtures of these isomers, 1-isocyanate-3,3,5-trimethyl-5-isocyanate methylcyclohexane, 2,4- and 2,6-hexahydrotolylene diisocyanate, as well as any desired mixtures of these isomers, hexahydro-1,3_ and / or -1,4-phenylene diisocyanate, perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate, 1,3 "and 1,4-phenylene diisocyanate, 2,4- and 2,4-tolylene diisocyanate and any desired mixtures of these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate, naphthylene-1,5 ~ 30 diisocyanate, triphenylmethane-4,4 ', 4 triisocyanate, polyphenylpolyethylene polyisocyanates, such as those obtained by aniline-formaldehyde condensation followed by phosgener and, m- and p-isocyanate-phenylsulfonylisocyanates, chlorinated aryl polyisocyanates, polyisocyanates containing carbodiimide groups, polyisocyanates containing 35 allophanate groups, polyisocyanates containing isocyanurate groups, polyisocyanates containing polyisocyanates, polyisocyanates containing aisocyanates ester groups, reaction products of the above-mentioned isocyanates with acetals and polyisocyanates containing polymeric fatty acid groups.

It is also possible to use the isocyanate group-containing distillation residues, as such or dissolved in one or more of the above-mentioned polyisocyanates, obtained during the industrial preparation of isocyanates. In addition, it is also possible to use any desired mixture of the above-mentioned polyisocyanates.

Generally, particular preference is given to the polyisocyanates which are readily available industrially, such as, for example, 2, k- and 2,6-tolylene diisocyanate and any desired mixture of these isomers ("TDI"), polyphenylpolymethylene polyisocyanates as prepared according to the aniline formaldehyde condensation followed by phosgenation ("crude MDI") and polyisocyanates containing carbodiimide, urethane, allo-fanate, isocyanurate, urea or biuret groups ("modified polyisocyanates").

The organic materials to be protected are preferably natural, semisynthetic or preferably synthetic polymers. Particular preference is given to thermoplastic polymers, special polyolefins, in particular polyethylene and polypropylene or copolymers thereof with mono- and diolefins.

Particular emphasis should be placed on the action of the new compounds against thermal and oxidative degradation, especially under thermal stress as it occurs during the processing of thermoplastic materials. The new components (b), (c), (d) and (e) are therefore extremely suitable for use as processing (in-process) stabilizers.

The mixture of components (b), (c), (d) and (e) is also suitable for stabilizing polyolefins in prolonged contact with extraction media.

Component (b) is preferably added in an amount of 0.0005 to 5%, in particular 0.001 to 2%, for example 0.01 to 2%, based on the weight of the organic material to be stabilized, to the organic to be stabilized material added.

Components (c), (d) and (e) are judiciously in an amount of 0.01 to 10%, for example 0.01 to 5%. it is preferably added 0.025 to 3%, in particular 0.025 to 1%, based on the weight of the organic material to be stabilized, to the 1008373 67 organic material to be stabilized.

In addition to components (a), (b), (c), (d) and (e), the new compositions may comprise further costabilizers (additives), such as, for example, the following: 5 1. Antioxidants 1.1 Alkylated monophenols, for example 2.6 -di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n -butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl- 4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols, such as eg 2,6-Dinonyl-4-methyl-phenol, 2,4-diroethyl-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 thereof.

1.2 Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthio-methyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.

1Λ Hydroquinones and alkaline hydroquinones. for example, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6- di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3.5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis- (3,5 di-tert-butyl-4-hydroxyphenyl) adipate.

25 1.4 Tocopherols. for example, α-tocopherol, β-tocopherol, γ-tocopherol, ó-tocopherol and mixtures thereof (vitamin E).

1.5 Hydroxylated thiodiphenyl ethers. for example 2,2'-thio-bis (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 Alkylidene bisphenols. for example 2,2'-methylene bis (6-tert-butyl-4-methylphenol), 2,2'-methylene bis (6-tert-butyl-4-ethylphenol), 2,2'-methylene bis [4-methyl-6- (α-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'-ethylidene bis (4,6-di-tert-butylphenol), 2,2'-ethylidene bis (6-tert-butyl-4-isobutylphenol), 2,2'- methylene bis [6- (α-methylbenzyl) -4-nonyl-1008373 68 phenol], 2,2'-methylene bis [6- (α, α-diraethylbenzyl) -4-nonylphenol], 4,4'-methylene bis (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 & 5 tris (5-tert-butyl -4-hydroxy-2-methylphenyl) butane, 1,1 -bis- (5 "tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3,3" bis (3'-tert-buty1-4'-hydroxyphenyl) butyrate ], bis (3 "tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadi a, bis [2- (3'-tert-butyl-2 '-hydroxy-5' -methylbenzyl) -6-ter t-buty 1-4-methyl phenyl] teref ta-10, 1,1-bis ( 3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3.5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2- methyl phenyl) -4-n-dodecyl mercaptobutane, 1,1,5.5 "tetra (5" tert-butyl-4-hydroxy-2-methylphenyl) pentane.

1.7 0-. N and S benzyl compounds. for example, 3.5.3 ', 5' "tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5" di-tert-butyl- benzyl mercaptoacetate, 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) -hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

1.8 Hydroxylated malonates. for example dioctadecyl-2,2-bis {3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecyl mercaptoethyl-2, 2-bis (3,5-di-tert-butyl-4-hydroxybenzyl] malonate, di [4- (1,1,3,3 "tetramethylbutyl) phenyl] -2,2-bis (3.5" di-tert-butyl -4-hydroxybenzyl) malonate.

l.Q Aromatic hydrogen hydroxide compounds. for example, 1.3.5 "tris (3.5" di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5 "di-tert-butyl-4-hydroxybenzyl) -2 , 3,5,6-tetramethylbenzene, 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-hydroxyanilino) -1,3.5 "triazine, 2-octylmer-capto-4,6-bis (3.5" di- tert-butyl-4-hydroxyanilino) -1,3.5 "triazine, 2-octyl mercapto-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, 1,3,5,5" tris (3.5 "di-tert-butyl-4-hydroxybenzyl) 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-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1008373 69 1,3.5 "tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate .

1.11 Benzyl phosphonates. for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5 "di-tert-butyl-1-hydroxybenzylphosphonate, 5 dioctadecyl-5-tert-butyl-1-hydroxy-3-nonhylbenzylphosphonate, the Ca salt of the monoethyl ester of 3-5 di-tert-butyl-hydroxybenzylphosphonic acid.

1.12 Acvlaminophenols. e.g. 1-hydroxylauric anilide, 4-hydroxystearic anilide, N- (3,5-di-tert-butyl-4-hydroxyphenyl) -10-carbamic octyl ester.

1.13 Esters of 6- (3.5-di-tert-butyl - * - - - hydroxydenyl) propionic acid with mono- or polyhydric alcohols, such as e.g. with methanol, ethanol, n-octanol, iso-octanol, octadecanol, 1,6-hexanediol, 1,9_nanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxyethyl ) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3 "thiaundecanol, 3" thiapentadecanol, trimethylhexanediol, trimethylol-propane, 1-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.1 ^ Esters of 6- (5-tert-butyl-3-hydroxyl-3-methylphenyl) propion-20 acid with mono- or polyhydric alcohols, such as e.g. with methanol, ethanol, n-octanol, iso-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thio-diethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl ) isocyanurate, N.N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3 "thiapentadecanol, trimethylhexanediol, trimethyl olpropane, il-hydroxymethyl-1-phospha-2,6,7" trioxabicyclo [2.2.2] -octane.

1.15 Esters of S- (3,5-dicvclohexvl-tt-hvdroxvfenvl) propionic acid with mono- or polyhydric alcohols, such as 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) oxalic acid diamide, 3-thiaundecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethylolpropane, -hydroxy-methyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.16 Esters of 3.5-di-tert-butyl-2-hydroxyl-phenyllazic acid with mono- or polyhydric alcohols, such as e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9 ~ nonanediol, ethylene glycol, 1008373 70 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate , N.N'-bis (hydroxyethyl) oxalic acid diamide, 3 "thiaundecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxy-5-methyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane .

1.17 Amides of B-n.5-di-tert-butyl-4-hydroxylphenyl) propionic acid.

such as e.g. N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexa-methylenediamine, N, N'-bis (3.5 ~ di-tert-buty1-4-hydroxyphenylpropionyl) trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenyl-propionyl) hydrazide, N. N'-bis [2- (3- [3.5-di-tert-butyl-4-hydroxyphenyl] pro- pionyloxy) ethyl] oxamide (Naugard® XL-1, supplied by Uniroyal).

1.18 Ascorbic Acid (Vitamin C).

1.10 Amine antioxidants. such as e.g. N.N'-diisopropyl-p-phenylene-diamine, N, N'-di-sec-butyl-p-phenylenediamine, N.N'-bis (1,4-dimethyl-15-pentyl) -p-phenylenediamine, N , N '- bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, - N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N.N 1'-diphenyl-p-phenylenediamine, N, N'-di (naphthyl-2) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N 1-phenyl-p-phenylenediamine, N- (1-20 methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfonamido) diphenylamine, N. N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldi phenylamine, 4-isopropoxy diphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenyl-25 amine, eg p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di (4-methoxyphenyl) amine, 2,6-di-tert-butyl -4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diamino-diphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1.2-30 di [(2- methylphenyl) amino] ethane, 1,2-di (phenylamino) propane, (o-tolyl) -biguanide, di [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1- naphthylamine, mixture of mono- and di-alkylated tert-butyl / tert-octyldiphenylamines, mixture of mono- and di-alkylated nonyldiphenylamines, mixture of mono- and di-alkylated dodecyl-diphenylamines, mixture of mono- and di-alkylated isopropyl / isohexyldiphenylene amines, mixture of mono- and di-alkylated tert-butyldiphenylamines, 2,3-dihydro-3,3 "dimethyl-4H-1,4-benzothiazine, phenothiazine, mixture of mono and di-alkylated tert-butyl / tert - 1008373 71 octylphenothiazines, mixture of mono- and di-alkyl erde tert-octyl-phenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diamino-but-2-ene, N, N-bis (2,2,6,6-tetramethylpiperid 4-yl) hexamethylenediamine, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2,6,6-tetramethyl-5-piperidin-4-one, 2,2,6, 6-tetramethylpiperidin-4-ol.

2. UV absorbers and light protectors 2.1 2- (2'-hydroxyphenyl) benztriazoles. such as, for example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'5'-di-tert-butyl-2 '-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl- 2'-hydroxyphenyl) benzo triazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzo triazole, 2- (3', 5'-di-tert -butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotazole, 2- (3'-sec- butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2 2- hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis- (a, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - ( 2-octyl-oxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- ( 3'-tert-butyl-21-hydroxy-5 '- (2-methoxycarbonylethyl) -20 phenyl) -5-chlorobenzotriazole, 2- (31-tert-butyl-2'-hydroxy-5 * - (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5'- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) 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-benztriazol-2-ylphenol]; the transesterification product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH2CH2-C00-CH2CH2] 2- with R = 3'-tert-butyl-4 '-hydroxy-5'-2H-benzo-triazol-2-ylphenyl, 2- [2'-hydroxy-3' - (α, α-dimethylbenzyl) -5 '"(1 * 1 * 3 * 3" tetramethylbutyl) phenyl] benzotriazole; 2- [2'-Hydroxy-3 '- {1,1,3,3-tetramethylbutyl) -51 - (α, α-dimethylbenzyl) phenyl] benzotriazole.

2.2 2-hydroxyl benzophenones. such as, for example, the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4-trihydroxy and 2'-hydroxy-4 .4'-dimethoxy derivative.

2 Λ Esters of optionally substituted benzoic acids. such as, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, 1008373X, 72 benzoylresorcinol, 3,5-di-tert-butyl-hydroxybenzoic acid-2,4 di-tert-butylphenyl ester, 3,5-di "tert-butyl-1-hydroxybenzoic acid hexadecyl ester, 3,5-di-tert-butyl-1-hydroxybenzoic acid octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid-2 -methyl-4,6-di-tert-butylphenyl ester.

5 2 Λ Acrvlaten. such as, for example, α-cyano-β, β-diphenylacrylic acid ethyl ester, respectively. isooctyl ester, α-carbomethoxy cinnamic acid methyl ester, α-cyano-p-methyl-p-methoxy cinnamic acid methyl ester, respectively. -butyl ester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N - ((--carbomethoxy-β-cyanovinyl) -2-methylindoline.

10 2.5 Nickel bonding. such as, for example, nickel complexes of 2,2'-thiobis [4- (1,1,3,3-tetramethylbutyl) phenol], such as the 1: 1 or 1: 2 complex, optionally with additional ligands, such as n-butylamine , triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithio-carbamate, nickel salts of the monoalkyl esters, eg the methyl or ethyl ester, of 4-hydroxy-3.5 "di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenylundecyl-ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with extra ligands.

2.6 Sterically hindered amines. such as, for example, bis (2,2,6,6-20 tetramethylpiperidin-1-yl) sebacate, bis (2,2,6,6-tetramethylpiperidin-1-yl) succinate, bis (1, -6) -pentamethylpiperidine - ^ - yl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidine - *) - yl) sebacate, n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonic acid bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) ester, the condensation product of 1- (2-hydroxyethyl) -2,2,6,6,6-tetramethyl-ii-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3.5-s-triazine, tris (2.2, 6,6-tetraroethyl-1-piperidyl) nitrilo-triacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,2-butane-tetracarboxylate, 1,1 '- ( 1,2-ethanediyl) bis (3, 3, 5, 5-tetramethyl-piperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, A-stearyloxy-2.2.6.6-tetramethylpiperidine, 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-triazaspirofA. 5] decane-2, t-dione, bis (1-35 octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, linear or cyclic condensation products of N , N'-bis (2,2,6,6-tetramethyl-1-piperidyl) hexa-methylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensation product of 2 -chloro-4,6-di (4-n-butylamino-2,2,6,6-tetra-methylpiperidyl) -1,3.5 "triazine and 1,2-bis (3-aminopropylamino) ethane, the condensation product of 2 -chloro-4,6-di (4-n-butylamino-1,2,6,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) -5 ethane, 8- acetyl-3-dodecyl-7,7,9,9 "tetramethyl-1,3,8-triazaspiro- [4. 5] decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1.2, 2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, the condensation product of N.N ' bis-10 (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexyl-amino-2,6-dichloro-1,3,5 "triazine, the condensation product of 1,2-bis ( 3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5 "triazine, as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]) N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N-15 {1,2,6,6,6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 2- undecyl- 7.7.9.9 "tetramethyl-1-oxa-3.8-diaza-4-oxospiro [4,5] decane, the 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) ethylene, N.N'-bis- 20 formyl-N, N 'bis (2,2,6,6-tetrame thy 1-¾-piperidyl) hexamethylenediamine, diester of 4-methoxymethylene malonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxy-4- (2,2,6,6- tetramethyl-4-piperidyl)] siloxane, reaction product of maleic anhydride α-olefin copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-25 pentamethyl-4-aminopiperidine.

2.7 Oxalic acid diamides. such as, 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 the mixture thereof with 2-ethoxy-2 ' -ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy as well as o- and p-ethoxy-di-substituted oxanilides.

2.8 2- (2-hydroxylphenyl) -1.8.5-triazines. such as, for example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3.5 "triazine, 2- (2-hydroxy-4-octyl-oxyphenyl) -4,6-bis (2,4- dimethylphenyl) -1,3.5 "triazine, 2- (2,4-dihydroxy-phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3.5" triazine, 2,4-bis (2-hydroxy- 4-propyloxyphenyl) -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-4-1008373 74 \

/ N

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 (2,1-dimethyl) -1,3,5 "triazine, 2- [2-hydroxy-1- (2-hydroxy-3-octyloxypropyl-oxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyl- oxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3.5 "triazine, 2- [2-hydroxy-4- (2-hydroxy-3" dodecyloxy-propoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1,3 .5 ~ triazine, 2- (2-hydroxy-4-10 methoxyphenyl) -4,6-diphenyl-1,3,5 ~ triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2 -hydroxypropoxy) 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-hydroxy-propyloxy] phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

15 3. Metal deactivators. such as, for example, Ν, Ν'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N.N'-bis (salicyloyl) hydrazine, N, N'-bis (315-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-sali-cyloylamino-1,2,4-triazole, bis (benzylidene) oxalyldihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N. N'-diacetyl-20 adipoyldihydrazide, N, N'-bis (salicyloyl) oxalyldihydrazide , N'-bis- (salicyloyl) thiopropionyl dihydrazide.

4. Phosphites and Phosphonites. such as, for example, triphenylphosphite, diphenylalkylphosphites, phenyl dialkylphosphites, tris (nonylphenyl) phosphite, trilaurylphosphite, trioctadecylphosphite, distearylpentaerythritol diphosphite, 2,4-butylphenylphosphol (2,4-butylphenyl) phosphite) di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methyl-phenyl) pentaerythritol diphosphite bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8 10-tetra-tert-butyl-12H-dibenz [d, g] -1,2,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [ d, g] -1,3-dioxafos focine, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethylphosphite, 2,2 ', 2 "-nitrilo [triethyltris (3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2-eth ylhexyl (3.3'.5.5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite.

5. Hvdroxvlamines. such as, for example, Ν, Ν-dibenzylhydroxylamine, 1008373 75 Ν, Ν-diethylhydroxylamine, Ν, Ν-dioctylhydroxylamine, Ν, Ν-dilauryl-hydroxylamine, Ν, Ν-ditetradecylhydroxylamine, Ν, Ν-hydroxydecyldecyl-hydroxydecyl N-hexadecyl-N-octadecylhydroxyl-amine, N-heptadecyl-N-octadecylhydroxylamine, NN-dialkylhydroxylamine 5 from hydrogenated tallow fatty amine.

6. Nitrons, such as, for example, N-benzyl-alpha-phenyl-nitron, N-ethyl-alpha-methyl-nitron, N-octyl-alpha-heptyl-nitron, N-lauryl-alpha-undecyl nitron, N-tetradecyl-alpha-tridecyl nitron, N-hexadecyl alpha pentadecyl nitron, N-octadecyl alf a-heptadecyl nitron, N-hexadecyl alpha heptadecyl nitron, N-octadecyl alpha pentadecyl nitron, N-heptadecyl alpha heptadecyl nitron, N-octadecyl-alpha nitronyl-alpha of Ν, Ν-dialkylhydroxylamine prepared from hydrogenated tallow fatty amine.

7. Thio-energists. such as, for example, thiodipropionic acid di-lauryl ester or thiodipropionic acid distearyl ester.

8. Peroxide-destroying compounds, such as, for example, esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mer captobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl tertiary trisulphitol, 20 (fi-dodecyl mercapto) propionate.

Q. Stabilizers for polyamide, such as, for example, copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

10. Basic costabilizers. such as, for example, melamine, poly-vinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg behenate, Mg stearate, Na ricinoleate, K palmite, antimony pyrocatecholate or zinc pyrocatecholate.

11. Nucleating agents, such as, for example, inorganic substances, such as e.g. talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably alkaline earth metals; organic compounds such as mono- or polycarboxylic acids, as well as co-salts thereof, such as e.g. t-butyl benzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymers, such as e.g. ionic copolymers ("ionomers").

12. Fillers and reinforcing agents, such as, for example, calcium carbonate, silicates, glass fibers, glass balls, asbestos, talc, 1008373 76 / kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers from other natural products , synthetic fibers.

1λ. Other additives, such as, for example, plasticizers, lubricants, emulsifiers, pigments, rheology additives, catalysts, reducing agents, optical brighteners, flame retardants, anti-static agents and blowing agents.

For example, the costabilizers are added in concentrations of 0.01 to 10% based on the total weight of the organic material to be stabilized.

For example, the fillers and reinforcing agents (item 12 of the list), for example talc, calcium carbonate, mica or kaolin, are added to the polyolefin in concentrations of 0.01 to 10%, based on the total weight of the polyolefin to be stabilized. .

The fillers and reinforcing agents (item 12 of the list), for example metal hydroxides, in particular aluminum hydroxide or magnesium hydroxide, are, for example, in concentrations of 0.01 to 60%, based on the total weight of the polyolefin to be stabilized, added to the polyolefin.

Carbon black as a filler is judiciously added to the polyolefin at concentrations of 0.01 to 5% based on the total weight of the polyolefin to be stabilized.

Glass fibers as reinforcing agents are judiciously added to the polyolefin in concentrations of 0.01 to 20% based on the total weight of the polyolefin to be stabilized.

Further preferred compositions comprise, in addition to components (a) to (e), other additives, such as in particular alkaline earth metal salts of higher fatty acids, for example calcium stearate.

As a conventional stabilizer combination for processing organic polymers, for example polyolefins, to form corresponding moldings, the combination of a phenolic antioxidant with a secondary antioxidant based on an organic phosphite or phosphonite is recommended. However, depending on the particular substrate and process involved, many polyolefin processors are forced to operate processes in the high temperature range above about 280 ° C. The inclusion of a new 1008373 77 processing stabilizer mixture of components (b), (c), (d) and (e), which is particularly suitable for high temperature applications, especially in the temperature range above 300eC, allows industrial materials and moldings based on, for example, high-density polyethylene, such as pipes and their technical variants (appendages), are produced at a faster speed and with fewer rejections. Another advantage of this stabilizer mixture is that it can be used in very small amounts. This leads to a decrease in the total antioxidant concentration over conventional stabilizer mixtures. Thus, the use of a low concentration of a stabilizer of the benzofuran-2-on type [component (b)] allows a reduction of the total stabilizer concentration by, for example, about one third in terms of polyolefins, which at the same time represents an economic advantage. .

The incorporation of components (b), (c), (d) and (e), and, if desired, further additives, into the organic polymer is done by known methods, for example before or during molding, or otherwise by application of the dissolved or dispersed stabilizer mixture on the organic polymer, with or without subsequently evaporating the solvent. The stabilizer mixture of the components (b), (c), (d) and (e) with or without further additives can also be added in the form of a master composition, these components being, for example, in a concentration of 2.5 to 25. % by weight based on the materials to be stabilized.

The stabilizer mixture of components (b), (c), (d) and (e), with or without further additives, can also be added before or during the polymerization or before cross-linking.

The stabilizer mixture of components (b), (c), (d) and (e), with or without further additives, can be incorporated in the organic material to be stabilized in pure form or encapsulated in waxes, oils or polymers.

The stabilizer mixture of components (b), (c), (d) and (e), with or without further additives, can also be sprayed onto the polymer to be stabilized. It can dilute other additives (e.g. the usual additives shown above) or their melts so that they can also be sprayed on the polymer to be stabilized together with these additives. The addition of 1008373 78 by spraying during the deactivation of the polymerization catalysts is particularly advantageous because it is possible to carry out the spraying using, for example, the steam used for the deactivation.

For example, in the case of spherically polymerized polyolefins, it may be advantageous to spray-coat the stabilizer mixture of components (b), (c), (d) and (e), with or without other additives.

The materials stabilized in this way can be used in a wide variety of ways, such as, for example, as films, fibers, tapes, moldings, profiles or as binders for coating materials, in particular powder coatings, adhesives or fillers.

The polyolefins stabilized in this way can be used in a corresponding number of ways in a corresponding manner, in particular as thick-layer polyolefin moldings which are in prolonged contact with extraction media, such as, for example, pipes for liquids or gases, films, geomembranes, strips, profiles or vessels.

The preferred thick layer polyolefin moldings have a layer thickness of 1 to 50 mm, in particular 1 to 30 mm, for example 2 to 10 mm.

As already mentioned, the organic materials to be protected are preferably organic, in particular synthetic polymers. In this context, thermoplastic materials are protected with particular advantage. In this context, particular attention should be paid to the excellent activity of the new stabilizer mixture of components (b), (c), (d) and (e) as in-process stabilizers (heat stabilizers). For this purpose, they are advantageously added to the polymer before or during processing. However, other polymers (e.g. elastomers) or lubricants or hydraulic fluids against degradation, e.g., light-induced or thermal-oxidative degradation, may also be stabilized. Elastomers can be derived from the above list of possible organic materials.

The respective lubricants and hydraulic fluids are based, for example, on petroleum or synthetic oils or on mixtures thereof. The lubricants are known to those skilled in the art and are described in the relevant technical literature, e.g., in Dieter Klamann, "Schmierstoffe und verwandte Produkte" (Verlag Chemie, Weinheim, 1982), in Schewe-Kobek, "Das Schmiermittel-Taschenbuch" (Dr. Alfred Hüthig-Verlag, Heidelberg, 197 * 0 and in "Ullmanns Enzyklopadie 5 der Technischeen Chemie", part 13, pages 85 ~ 9 * 4 (Verlag Chemie, Weinheim, 1977) ·

A preferred embodiment of the present invention therefore relates to the use of components (b), (c), (d) and (e) as stabilizers, in particular in-process stabilizers (thermal stabilizers), for organic materials , especially thermoplastic polymers, against oxidative, thermal or light-induced degradation.

The present invention also relates to a stabilizer mixture comprising (i) at least one compound of the benzofuran 2-15 on type, (ii) at least one compound from the group of the organic phosphites or phosphonites, (iii) at least one compound from the group of the phenolic antioxidants and (iv) comprises at least one compound from the group of the sterically hindered amines.

Also preferred are stabilizer mixtures in which the weight ratio of components (i) :( ii) :( iii) :( iv) 10: 1: 1: 0.1 to 0.01: 1: 10: 100, in especially 5: 1: 1: 0.1 to 0.01: 1: 1: 10.

The new stabilizer mixture of components (b), (c), (d) and (e) is characterized by excellent hydrolysis stability and advantageous coloring behavior, i.e. little discoloration of the organic material during processing.

Organic materials stabilized with the components of the present invention are particularly well protected against light-induced degradation.

The present invention also relates to a method of stabilizing an organic material against oxidative, thermal or light-induced degradation, which incorporates or applies to the material at least one of each of the components (b) , (c), (d) and (e).

Preference is given to a method of stabilizing polyolefins which are in prolonged contact with extraction media, wherein the polyolefins are thick layer polyolefin moldings and have a layer thickness of 1 to 50 mm, in particular 1 to 30 mm, for example, 2 to 10 mm, which includes incorporating into the polyolefins or applying to the 1008373 80 polyolefins at least one of each of components (b), (c), (d), and (e).

Also of particular interest is a stabilization method of thick layer polyolefin moldings which are in prolonged contact with extraction media, the thick layer polyolefin moldings being pipes or geomembranes, which incorporate into the moldings or apply at least one of each of the moldings to the moldings components (b), (c), (d) and (e).

The term geomembranes refers to films which, for example, are used on landfills and which should have a life of up to 300 years.

Extraction media are, for example, liquid or gaseous inorganic or organic materials.

Examples of gaseous inorganic materials are oxygen; Nitrogen; oxides of nitrogen; for example NO, laughing gas or NO2; oxides of sulfur, for example sulfur dioxide; halogens, for example fluorine or chlorine; Bronzed acids, for example hydrogen fluoride, hydrochloric acid, hydrogen bromide, hydrogen iodide or hydrogen cyanide; or bases, for example ammonia.

Examples of gaseous organic materials are C 1 -C 1, alkanes, for example methane, ethane, propane or butane; carbon monoxide; carbon dioxide; or phosgene.

Examples of liquid inorganic materials are water, chlorinated drinking water or aqueous salt solutions, for example a sodium chloride solution (brine) or sodium sulfate solution; bromine; acid halides, e.g. titanium tetrachloride, thionyl chloride, nitosyl chloride or trimethylsilyl chloride; bases, for example a solution of sodium hydroxide (NaOH) in water, a solution of potassium hydroxide (Κ0Η) in water, a solution of ammonia in water, a solution of sodium hydrogen carbonate in water or a solution of sodium carbonate in water.

Examples of liquid organic materials are organic solvents or liquid organic reagents.

Examples of organic solvents are aliphatic hydrocarbons, for example pentane, hexane, heptane, octane, soluble gasoline, nonane or decane; alcohols, for example, methanol, ethanol, isopropanol, butanol, pentanol, amyl alcohol, cyclohexanol, pentaerythritol, ethylene glycol, ethylene diglycol, methyl cellosolve, polyethylene glycol or glycerol; ketones, for example acetone, diethyl ketone, methyl ethyl ketone, diphenyl ketone or cyclohexanone; ethers, for example diethyl ether, dibutyl ether, tetrahydrofuran or dioxane; aromatic hydrocarbons, for example benzene, toluene or xylene; Heterocyclic solvents, for example furan, pyridine, 2,6-lutidine or tiophene; dipolar aprotic solvents, for example dimethylformamide, diethyl acetamide or acetonitrile; or surfactants.

For the purposes of the present invention, extraction media are also mixtures and solutions, especially aqueous mixtures, emulsions or solutions, of the above-mentioned liquid or gaseous inorganic and organic materials.

Of particular interest are those extraction media, which are important in the chemical industry or in landfills.

A preferred embodiment of the present invention therefore also relates to the use of a stabilizer mixture of components (b), (c), (d) and (e), with or without further additives, to improve the stability of polyolefins in prolonged contact with extraction media.

The preferred components (b), (c), (d) and (e) for use as stabilizers, the stabilization method and the stabilizer mixture are the same as those described for the organic material compositions.

The invention is illustrated in more detail in the following examples. Parts and percentages are by weight.

Example I: Stabilization of polyethylene that is in prolonged contact with water.

0.1 wt.% Calcium stearate and the stabilizers listed in Table A are added dry to a polyethylene polymer (Hostaler® CRP 100; PE-HD) directly from the reactor, and the additives are stirred for two minutes ( examples Ia-Ic) in a Pappenmaier mixer (type 20) incorporated therein.

1008373 82

Table A:

Examples Stabilizers Quantity (wt%)

Irgafo ^ S) 168c 0.10

Example Iaa) Irgano® 1010d) 0.10

Chimassort® 9 ^ 4'1 0.20 5 Compound (101) f> 0.05

Example Ibb> Irgafo ^ E) 168c 0.10

Irgano? ® I010d "0.05

Chimassort® 9 ^ ° 0.20

Compound (101) r> 0.05

Example 1cb) Irgafo® 168c) 0.10

Irgano® 1010d) 0.05

Chimassort® 119g> 0.20 10 a) Comparative example b) Example according to the invention c) IrgafoS® 168 (Ciba Spezialitatenchemie AG) is tris (2,1-di-tert-butylphenyl) phosphite.

d) Irgano® 1010 (Ciba Spezialitatenchemie AG) is the pentaerythritol ester of 3 ~ (3, 5-di-ter-butyl-1-hydroxyphenyl) propionic acid (compound of the formula Vlo).

e) Chimassort® 9 ^ (Ciba Spezialitatenchemie AG) refers to linear or cyclic condensation products prepared from N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 20 il-tert- octylamino-2,6-dichloro-1,3,5-triazine [compound of the formula (H5)].

f) Compound (101) is a mixture of about 85 parts by weight of the compound of formula Va and about 15 parts by weight of the compound of formula Vb.

25 g) Chimassort® 119 (Ciba Spezialitatenchemie AG) refers to condensation products prepared from 2-chloro-il, 6-di (il-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1, 3.5-triazine and 1,2-bis (3-aminopropylamino) ethane [compound of the formula (H6)].

Irgafo® 168, Irgano®® 1010, Chimassort® 9 ^ and Chimassort® 119 1008373 83 are protected trade names of Ciba Spezialitëtenchemie AG.

The stabilized polyethylene is homogenized at 220 ° C in a Schwaben-than extruder and granulated at 300 ° C. For the extraction experiments in water, test sheets measuring 1 * 1 mm by 20 mm by 2 mm of the granules of the individual formulations (Examples 1a-Ic) are pressed using a press bench. To simplify the removal of the test sheets from the mold, pressing between two aluminum sheets is performed.

The stabilizer extraction experiments were performed with deionized water. The thermal conditioning of the extraction vessels takes place in a convection oven from Heraeus (Hanau, Germany) with a maximum temperature deviation of 1.5 ° C. Glass vessels are used for the extraction experiments at a temperature lower than the boiling point of water. In the case of a water temperature of 105 ° C, stainless steel pressure vessels are used. Because of the risk of supersaturation of the water with stabilizer, the amount of liquid for the experiments is adjusted to about * 100 ml for about 70 g of polymer and the water is replaced with 20 fresh water at regular intervals, especially after each sampling.

The test sheets are exposed to the experimental conditions described above at 80 ° C for 50 days. At the end of the extraction experiments, the residual stabilizer content and the oxidation induction time (0IT) of the test sheets are measured.

The residual content of the sterically hindered phenol, Irgano> ® 1010, is determined using an internal standard in a Spectra Physics SP 8800 HPLC instrument with autosampler and Spectra 200 UV / VIS detector. The chromatography is performed at room temperature with a column of the hyperchrome 125 x * 1.6 30 mm type, filled with Nucleosil C 185 µm. The injection volume is 1 * 1 μΐ at a flow rate of 1.5 ml / minute. UV detection takes place at 27Ο nm.

The residual content of the triazine containing sterically hindered amines, Chimassort® 9 ^ and Chimassort® 119, is determined with a UV-35 spectrometer of the type Perkin Elmer Lambda 15. by the difference between the absorptions at 2 ** 6, * 1 and Measure 300 nm.

The oxidation induction time is determined using a "DuPont instrument 910 differential scanning calorimeter" from TA Instruments 1008373 84 (Alzenau, Germany) and sample amount from 5 to 10 mg, and describes the period, in minutes, under constant thermal voltage (190 ° C / 02) until complete decomposition of the polyethylene sample begins. The longer the oxidation induction time, the better the stabilization of the polyethylene and the more stable the polyethylene with respect to extracted water in prolonged contact with the polyethylene.

The results show that the stability of polyolefins in prolonged contact with extracted media is improved when the stabilizer mixture comprises a new component (b), (c), (d) and (e). The results are summarized in Table B.

Table B: Storage of water for 50 days at 80 ° C

Example Stabilizer Residual Static Oxidation Inbilizer Halide Time In After 50 Days Minutes

at 80 ° C

15 0.10% IrgafoS © l68c "

Iaa '0.10% Irganok® 1010d) 52% 34 0.20% ChimassorbS) 944e) 57% 0.05% compound (101) n Ibb) 0.10% Irgafoö® l68c' 0.05% Irganok® 1010d) 56% 38 0.20% Chimassorb® 944e> 71% 0.05% compound (101) f) 20 Icb) 0.10% Irgafoö® l68c> 0.05% Irganok® 1010d) 57% 39 0.20% Chimassorb ® 1198 '70%

Footnotes a) to g) see table A.

Example II: Stabilization of polypropylene in the case of multiple extrusion and at particularly high temperatures.

1.5 kg polypropylene powder (Profak® 6501), initially stabilized with 0.008% Irganok® 1076 (compound of formula VIb) (with a melt index of 3.2, measured at 230 ° C and below 2.16 kg) 1008373 85 is mixed with 0.10 # of calcium stearate and 0.015 to 0.20 # of the stabilizers listed in Table C. This mixture is extruded at 100 revolutions per minute in an extruder with a housing diameter of 20 mm and a length of 400 mm, the maximum temperature of the extruder being set at 280, 300, 320 and 340 ° C. The extrudate is drawn through a water bath for cooling 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 indicates a large chain breakdown and thus poor stabilization. The results are summarized in Table C. It shows that the stability of polypropylene is improved when the stabilizer mixture comprises a new component (b), (c), (d) and (e).

15 Table C:

Example Stabilizers Quantity Melt Index after (wt. #) 5 extrusions

Irgafo ^ ® 168c) 0.10

Example Ilaa) Irgano> ® 1010d) 0.10 17.5

Chimassort® 944e) 0.20

Compound (101) n 0.015 20 Example IIbbl Irgafos® 168 ° 0.10 8.6

Irganox® 1010d) 0.05

Chimassort® 944'1 0.10

Compound (101) n 0.015

Example IIcb) Irgafo ^ D168c) 0.10 8.0

Irganox® 1010d), 0.05

Chimassort® 119g) 0.10

Footnotes a) to g) see Table A of Example I.

1008373

Claims (52)

A composition comprising a) an organic material that is subject to oxidative, thermal or light-induced degradation, b) at least one compound of the benzofuran-2-one type, c) at least one compound from the group of the organic phosphites or phosphonites, d) at least one compound from the group of the phenolic antioxidants and e) at least one compound from the group of the sterically hindered amines. 2. A composition according to claim 1, comprising as component (b) a compound of the formula I O P "Λ / Re 20 JL jl R '(i) R4 n 25 where, when η is 1, Rj is unsubstituted or with C 1 -C 4 alkyl, C 1 -C 1 alkoxy, C 1 -C 3, alkylthio, hydroxyl, halogen, amino, C 1 -C 8 alkylamino phenylamino or di (C 1 -C 4 alkyl) amino substituted naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo [b] thienyl, naphtho [2,3-b] thienyl, thiantrenyl, dibenzofuryl, chromenyl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidynyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indolyl, indolyl -nyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, β-35carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazolyl, phenothiazolyl terphenyl, fluorenyl or phenoxazinyl, or Rt is a group of formula II 1008373 A: - Re and if η is 2, R 1 is unsubstituted or C 1 -C 4 alkyl or hydroxyl substituted phenylene or naphthylene; or ~ R 12 -X is ~ R 13 -, R 2, R 3. R 1 and R 3 independently of one another hydrogen, chlorine, hydroxyl, C 1 -C 12 alkyl, C 1 -C 9 phenylalkyl, unsubstituted or C 1 -C 6 alkyl substituted phenyl; unsubstituted or C 1 -C 8 alkyl substituted C 5 -C 8 cycloalkyl; Cj-Cjg alkoxy, Cj-Cl8 alkylthio, Cj-C *, alkyl-amino, di (Cj-C1, alkyl) amino, Cj-C25 alkanoyloxy, Cj-C2-alkanoylamino, C3-C25 alkenoyloxy, c3-c25 alkanoyloxy which interrupted by oxygen, sulfur, or NR4; C6-C9 cycloalkylcarbonyloxy, benzoyloxy or with C 1 -C 4 20 I are alkyl substituted benzoyloxy; or else the groups R2 and R3 or the groups R3 and RA or the groups R /, and R5, together with the carbon atoms to which they are attached, form a benzo ring, R *, additionally - (CH2) | -C0Rj5 or - (CH2 ) q0H is or, when R3, R5 and R6 are hydrogen, R ^ 25 is additionally a group of formula III "" Ί ^ "...... r17 wherein Rj is defined as shown above for n = 1 , R ^, hydrogen or a group of the formula IV is 1008373 O 0 \ r2vX / \ XYR, (IV) ζ ^ Λν. Λ • R3 7 r5 R4 10 where R /, is not a group of formula III and Rj is defined as shown above for n = 1, R7, R8, R9, R10 and Rn independently hydrogen, halogen, hydroxyl, Cj -C2; alkyl, C 2 -C 23 alkyl interrupted by oxygen, sulfur or N-R 3; C 1 -C 25 alkoxy, C 2 -C 25 alkoxy interrupted by oxygen, sulfur or N-R 4; C3-C25 alkylthio, C3-C25 alkenyl, C3-C2-alkenyloxy, C3-C25 alkynyl, C3-C25 alkynyloxy, C7-C9 phenylalkyl, C7-C9 phenyl-alkoxy, unsubstituted or substituted with Cj-Cz, alkyl phenyl; unsubstituted or C 1 -C 2 alkyl substituted phenoxy; unsubstituted or C 1 -C 8 alkyl substituted C 5 -C 8 cycloalkyl; unsubstituted or C 1 -C 20 alkyl-substituted C 5 -C 8 cycloalkoxy, diC 1 -C 2 alkyl) amino, C 1 -C 20 alkanoyl, C 3 -C 25 alkanoyl interrupted by oxygen, sulfur or N-R 2; C 1 -C 25 alkanoyloxy, C 3 -C 25 alkanoyloxy interrupted by oxygen, sulfur or N-Rlft; C 1 -C 25 alkanoylamino, C 3 -C 2 alkenoyl, C 3 -C 25 alkenoyl interrupted by oxygen, sulfur or N-Rh 2, C 3 -C 23 alkenoyloxy, C 3 -C25 alkenoyloxy interrupted by 35 I oxygen, sulfur, or N-R 3; C6 -C9 cycloalkylcarbonyl, C6 -C8 cycloalkylcarbonyloxy, benzoyl or benzyl substituted by C1 -C12 alkyl; ben-kOzoyloxy or C 1 -C 12 alkyl-substituted benzoyloxy; 1 008373 R18 O 820 821 - O - C - C - Rjr or - 0 - C - C - 0 - R2o, or else, in formula I II R19 R R22 II, the groups R7 and R8 or the groups R8 and Ru, together with the carbon atoms to which they are attached, form a benzo ring, R12 and Rj-j are independently unsubstituted or with C 1 -C *, alkyl substituted phenylene or naphthylene, R 11 is hydrogen or alkyl, R 11 is R 13 hydroxyl, R 10, C 1 -C 12 alkoxy or -N, 15 R 25 R 16 and R 17 are independently hydrogen, CF 3, C 1 -C 12 alkyl or phenyl, or R 18 and R 17, together with the C atom to which they are attached form a C3-C8 cycloalkylidene ring which is unsubstituted or substituted 1-3 times with C 1 -C 18 alkyl; R 18 and R 19 are independently hydrogen, C 1 -C 6 alkyl or phenyl, R 20 is hydrogen or C 1 -C 18 alkyl, R 2 hydrogen, unsubstituted or C 1 -C 6 alkyl-substituted phenyl; C 1 -C 25 alkyl, C 2 -C 25 alkyl interrupted by oxygen, 25 I sulfur or N-Rj / ,; C7-C9 phenylalkyl which is unsubstituted or substituted 1 to 3 times on the phenyl group with C 1 -C 4 alkyl; c7-c25 phenylalkyl which is unsubstituted or is substituted on the phenyl group 1-3 times with C 1 -C 18 alkyl and is interrupted by oxygen, sulfur or N-R 4. or else the groups R20 and R21, together with the carbon atoms to which they are attached, form a C12 -C12 cycloalkylene ring which is unsubstituted or substituted 1-3 times with C 1 -C 8 alkyl; R22 is hydrogen or C1 -C1 alkyl, R23 hydrogen, C1-C25 alkanoyl, C3-C25 alkenoyl, C3-C25 alkanoyl interrupted by oxygen, sulfur or N-R 2; C3 -C25 alkanoyl which is AO1 substituted with a di (C1 -C6 alkyl) phosphonate group; C6-C9 cycloalkylcarbonyl, thenoyl, furoyl, benzoyl or benzoyl substituted with C 1 -C 12 alkyl; 1008373 H3C. / CH 3 CH, n C H 3 C. / 3 ii _ / = 0Ha ii wc'ch »-C CSH - ΛΛ — OH '-c CH — S - CH2 — OH' 5. p π26 n26 ch3" HC / Η _ / "'CH, 0 0 0 10 π / ΓΛ ii ll or ii -C-CH-C-Q-OH '-CR-C-R28 -CR ^ -R30 ch3 r26 LJ 2 is 15, R2 / j and R2 - independently of each other hydrogen or Cj -C18 alkyl, R26 is hydrogen or C 1 -C 8 alkyl, R 27 is a direct bond, C 1 -C 18 alkylene, C 2 -C 18 alkylene interrupted by oxygen, sulfur or NR 2; C 2 -C 18 alkenylene, C 2 -C 20 alkylidene, C7-C20 phenylalkylidene, C3-C8 cycloalkylene, C 1 -C 8 bicycloalkylene, unsubstituted or C 1 -C 8 alkyl substituted phenylene or 25, R 2 / y R 28 hydroxyl, OO-MM j j. C 1 is -Cl 8 alkoxy or -N, r 25 is 35 0 I II R 2g oxygen, -NH- or N-C-NH-R 30, R 30 is C 1 -C 18 alkyl or phenyl, 40 R31 is hydrogen or C 1 -C 4 alkyl, M is an r-worthy metal cation, 1008373 X is a direct bond, oxygen, sulfur or -NR 3 J-, η is 1 or 2, p is 0, 1 or 2, q 1 , 2, 3, 4, 5 or 6, 5 r is 1, 2 or 3 and s is 0, 1 or 2. A composition according to claim 1, which comprises as component (b) a compound of the formula V 10 O (V) R, 20 wherein R 2 is hydrogen or C 1 -C 6 alkyl, R 3 is hydrogen, R /, is hydrogen or C 1 -C 6 alkyl, R 1 is hydrogen, R7, Rg, R9, R10 and Rn independently of one another are hydrogen, Ca-C 1-6 alkyl or C 1 -C 12 alkoxy, with the proviso that at least two of the groups R7, R8, Rg, R10 or Ru are hydrogen . 4. A composition according to claim 1, wherein component (b) is a compound of the formula Va or Vb 1008373 O O h3c. / CHa? Λ / "h3c ^ / ch3 9". 5 / cyYvvCH3 / cyYVvCH3 H3C l ^ vj) H3C Icv ^ yJ h3c-c-ch3 h3c-c-ch3 ch3 ch3 10 (Va) (Vb) or a mixture of is the two compounds of the formula Va and Vb A composition according to claim 1, comprising as component (c) a compound of the formula 1, 2, 5 or 6 O - R 'O-R' / / 20 (1) R't — 'Y' - Ρχ Α - (P) (2) O-R 'O-R' L 3J n-p— \ / —® 25 R ', - 0-p' VV — O-R ', (5) O -' '—O / “Ar” - E' - PZ ', s (6) \ W'15 O - (\ / V-R'u 35. Q 14 R 'L 14 Y y? 1008373 wherein n 'is 2 and y' is 1, 2 or 3; A 'is C 2 -C 18 alkylene, p-phenylene or p-biphenylene, E', when y 'is 1, is C 1 -C 18 alkyl, -OR'j or fluoro; 5 E ', if y' is 2, p-biphenylene, E ', if y' is 3, N is (CH2CH2O-) 3; R'j, R'2 and R'3 independently of one another are C 1 -C 18 alkyl, C 7 -C 9 phenylalkyl, cyclohexyl, phenyl or phenyl substituted with 1-3 alkyl groups having a total of 1-18 carbon atoms; R'19 / is hydrogen or C1 -C9 alkyl, R'19 is hydrogen or methyl; X 'is a direct bond, Y' is oxygen, Z 'is a direct bond or -CH (R'18) - and R' 16 is C 1-4 alkyl. The composition of claim 1, wherein component (c) tris- (2,1-di-tert-butylphenyl) phosphite, bis (2,1i-di-tert-butyl-6-methylphenyl) -ethyl phosphite or tetrakis (2 , ty-di-tert-butylphenyl), 4'-biphenylene diphosphonite. 7. A composition according to claim 1, which comprises as component (d) a compound of the formula VI, 1 HC 1 25 3 \ CH3 / C H3C \ _ / = \ (V) Η ° -Λ /) - X-- R2 R. Jn 30 wherein R 1 is C 1 -Calkyl, η is 1, 2, 3 or 4, 35 0 0 II II X is methylene, -CH2-CH2-CY- or -CH2-C-0-CH2-CH2- , Y is oxygen or -NH-; and when η is 1, 1008373 O II is X -CH 2 -CH 2 -C-Y-, wherein Y is attached to R 2 and R 2 is C 1 -C 12 alkyl; and 5 when n is 2, O II is X -CH 2 -CH 2 -C-Y-, wherein Y is bonded to R 2 and R 2 is C 2 -C 12 alkylene or C 1 -C 12 alkyl-10 interrupted by oxygen or sulfur; or, when Y is -NH-, R2 is additionally a direct bond; and when n is 3, 0 X is methylene or -CH 2 -C-O-CH 2 -CH 2 - wherein the ethylene group is attached to R 2 and t> vV ° R 2 is 1 I; and 20 / ΝγΝ ^ O if n is 4, 0 II is X - CH2 - CH2 - C - Y - where Y is attached to R2 and R2 is C4 -C10 alkane tetrayl. 8. A composition according to claim 7 wherein in the compound of formula VI, when η is 1, R 2 is crc 20 alkyl. The composition of claim 7. wherein in the compound of formula VI, when n is 2, R 2 is C 2 -C 8 alkylene or C 1 -C 8 alkylene interrupted by oxygen or sulfur; or, when Y is -NH-, R2 is additionally a direct bond; and when n is 4, R 2 is C 1 -C 8 alkane tetrayl. The composition of claim 7. wherein in the compound of formula VI 1008373 R 1 is methyl or tert-butyl, n is 1, 2 or 4, 0 II 5 X is -CH 2 -CH 2 -C-Y-, Y is hydrogen or -NH-; and when η is 1, R 2 is C 1 -C 12 alkyl; and if n is 2, R 2 is C 1 -C 6 alkylene or oxygen-interrupted C 1 -C 6 alkylene; and when n is ^, R2 is C / j-Cg alkane tetrayl. 11. A composition according to claim 1, wherein component (d) is at least one compound of the formula Vla, VIb, VIc or VId H, C \ H C-A O} = \ 11 20 HO — CH — CH — C— NH— (CHJ, - (y | a) h3c ^ / / ch3 H30 3 L 3 2 25 HaC 3 \ / CH3 HaC ^ V \ S HO— (v /) CH - CH — C — O — C18H37 (VIb) 30 H3C ^> c \ / CH3 h3c 3 35 1008373 H, C 3 \ / CH3 H ° - ^ \ _ J ~ 'CH-CHi-C-0-CH - C (V | C) HX ^ / C \ / CH, HX 3 L 3 J4 10 HX \ / CH3 Hc "C \ J} 15 HO — ά)> CH — CH —C — O — CH — CH —0 — CH2 - (Vld) · H3C L J 2 20 A composition according to claim 1, wherein component (e) comprises at least one group of the formula XII or XIII ch3g, ch3g, 25g-ch2 -LG; (XII) - \) <—NwN— G - CH ^ I G —CH2 ^ | ch3 ch3 (XIII) wherein G is hydrogen or methyl and Gj and G2 are hydrogen, methyl or together oxygen. 13. A composition according to claim 1, wherein component (e) is a compound of the formula H1, H2, H3. , H5. H6 or H7 1008373 5 'CH3 ch3 Η3 ° 9-λ fl s ACH3 h17c8o-n Vo-C- (CHz) -C-0- (N OC, H17 (H1) CH, CH, 10 (CH,) 3C \ _. "-ο, η, o I ^ ch, H0 <J> CH —C - C-0 ^ N CH3 (H2) <chac ΤΓ L 3 J 2 15 CH, CH3 Η3 ° \) _ Ι Ο O" LCH3 h3c-n \ -oc— (CH2) -c-0 / 'N-CH3 (H3) TCHs 20 CH3 ch3 ch3 LCH3 ο O / ~ \ II II --O (N-CH2-CH-0-C-CH-CH2-C - (H4) 25 P'CH, CH3 3 -> m 30 1008373 9H3 CH3 II 3 HN — C-CH-— C-CH, II 2 I 3 X CH3 ch3 5 N ^ N --U -N- (CH2) 6-N - (H5) NI 26 I v 'H3c-J Lch3 h3c— [Lch, HC) N ^ CH / N H3C I CH3 H3C I CH3 10 H 3 HL - * 01 R 'R' II R '- NH - (CH2) —N - (CH2) 2— N - (CH2) - NH - R' 15 ch3 I CH3 h3c-J_ n <^ n _Uch3 R '= H3C-f7 ^ -N-NQ-CH, (H6) 20 H3C n * C <H9 n'C <H9 I CH3 CH3 CH3 HN — CHXH.OH i 25 n-C4H9-N-UN -Nn-C4H9 H3C ^ OcCH3 H3C ^ 0cCH3 (H7) H3C γ ch3 H3C γ ch3 ^ 30 0 0 ό ό 35 1008373 where m is a number ranging from 2 to 200. 1 ^. A composition according to claim 1, comprising as component (a) a natural, semisynthetic or synthetic polymer. A composition according to claim 1, comprising as component (a) a thermoplastic polymer. The composition of claim 1, which comprises as component (a) a polyolefin. 17. A composition according to claim 1, comprising as component (a) polyethylene or polypropylene or a copolymer thereof with mono- and diolefins. The composition of claim 1, which comprises as component (a) a thick layer polyolefin molding. A composition according to claim 18, wherein the thick-layer polyolefin molding has a layer thickness of 1-50 mm. 20. The composition of claim 18, wherein the thick layer polyolefin molding comprises polyolefin tubing or polyolefin geomembranes. The composition of claim 1, comprising as component (a) a polyolefin which is in prolonged contact with extraction media. The composition of claim 21, wherein the extraction medium is a liquid or gaseous inorganic or organic material. The composition of claim 1, wherein component (b) is present in an amount from 0.0005 to 5%. based on the weight of component (a). 2k. The composition of claim 1, wherein the components (c), 1008373 (d) and (e) are present in an amount of 0.01 to 10% based on the weight of component (a). A composition according to claim 1, which in addition to components 5 (a), (b), (c), (d) and (e) also comprises further additives. 26. Stabilizer mixture comprising i) at least one compound of the benzofuran-2-one type, ii) at least one compound from the group of organic phosphonites or phosphonites, iii) at least one compound from the group of the phenolic antioxidants and iv) at least one compound from the group of the sterically hindered amines. 15 The stabilizer mixture according to claim 26, wherein the weight ratio of the components (i) :( ii) :( iii) :( iv) is 10: 1: 1: 0.1 to 0.01: 1: 10: 100. 28. A method of stabilizing an organic material against oxidative, thermal or light-induced degradation comprising incorporating or applying to the material at least one of each of components (b), (c), (d) and (e) according to claim 1. 25 The use of a mixture of the components (b), (c), (d) and (e) according to claim 1 as stabilizers for organic materials against oxidative, thermal or light-induced degradation. 1008373