GB2371543A - 3,3,5,5-Tetraalkyl-piperazine-2,6-dione stabilizers - Google Patents

Description

A-21559/A/CHM 103

- 1 Compositions Stabilized by Dioxopiperazinvl Derivatives / The invention relates to compositions based on polyoxymethylene, blends of polycarbonate with acrylonitrile-butadiene-styrene terpolymer, or functional acrylate resin and crosslinking agent, which are stabilized by addition of a compound of the class of 3,3,5,5-tetraalkyl-

piperazin-2,6-dione, new compounds of this class, the use of the novel compounds as stabilizers for organic material against harmful effects of light, oxygen and/or heat, and organic material stabilized correspondingly.

Structure and numbering of of 3,3,5,5-tetraalkyl-piperazin-2,6-dione is as shown in the H R::N:'R

formula: N O, with R being alkyl.

Preparation of some of the above compounds, specific derivatives thereof, and use of these compounds as stabilizers e.g. for polyethylene, polypropylene, nylon or ABS is shown, by T. Yoshioka et al., Bull. Chem. Soc. Jap. 45, 1855-1860 (1972); Luston and Vass, Makromol.

Chem., Macromol. Symp. (1989), 27; and in the documents US-A-4413096; C.A. 99:141068; ,. it- C.A.96:104191; US-A-3969316; US-A-3936456; US-A-3928357; US-A-3928330; US-A 3920659; US-A-3919234.

It has now been found, that certain compounds of the 3,3,5,5-tetraalkylpiperazin-2,6-dione ' class are especially well suitable as stabilizers for polyoxymethylene, blends of i, polycarbonate with acrylonitrilebutadiene-styrene terpolymer, or coatings based on a functional acrylate resin and a crosslinking agent.

The invention therefore pertains to a composition comprising (A) a synthetic organic polymer selected from the group consisting of polyoxymethylene, a blend of polycarbonate with acrylonitrile-butadienestyrene terpolymer, and a coating system based on a functional acrylate resin and a crosslinking agent, and (B) as stabilizer a compound of the formula I or 11

- 2 R1 R5-N N--A(1)

R:O s Z1- \ X R'15 X _

N: N R.:/ (11)

RAN-(R 9 C). R. 15 P

wherein p is from the range 1 to 10; s is from the range 1 to 8; when s is 1, A is C1-C18alkyi; C2-C18alkyl which is substituted by NH2, hydroxy, halogen and/or OR10 or interrupted by -O-, -NH- and/or -NR10-; or A is C,C18alkyl substituted by -COORS or phenyl; when s is 2, A is C2C10alkylene; C4-C12alkenylene; C3-C15alkylene substituted by one or more OH and/or interrupted by one or more oxygen, phenylene, C1C4alkylphenylene, -COO-, -CONH-, .. - X IN:r X N N. N, N ' N, -NH- and/or -ERG-; Z z N z when s is 3, A is C3-C10alkantriyl; C3-C,2alkantriyl substituted by OH and/or interrupted by oxygen, -NH- or -NR10-; or one of the groups of the formulae (Illa) - (Ilid)

- 3 R28 0 (Illa) O O R J:X, Ris R',5 X R / - (R8-CO) j- R's - X y N.:'XR4s iCO-R2s) j N:N (Illb) - (Rg-CO)j-R1s-x - tRg-CO)j-R,s - (R8-CO). RisN.: N n,X- R,siCO-R28)j N N z (Illc) Rl85 O (Ilid) RJ:X- '6 X2 R/

when s is 4, A is C4-C,Oalkantetryl; C4-C,2alkantetryl substituted by OH and/or interrupted by oxygen, -NH or -NR,o-; or one of the groups of the formulae (IVa) - (IVd)

Rl8iO x o 3 0 R J x 7-X2J'R / X4 (IVa) Rl29 - (R8-CO) j- R1s - X:,N::X-R', 5 -X:; N:, X - R 5 lCO-R8) j N:,N N)>N (IVb) - (Rg-CO)j-R1s-x x-R1s-(CORg) j-

- (Rg-CO)j-R1s - (R8-Co) - R1s - N., N.::X- R1s iCO-R28)j N N X- R1s5COR28)j- (IVc) - (Rg-Co)j-R1s R15 (CO-R28)i - (R8-CO) j- R1s - N.:: N.:: NR1s iCO-R28) j N N z (IVd) when s is 5, A Ts C5-C10alkanepentayl; Cs-C, 2alkanepentayl substituted by OH and/or interrupted by oxygen, -NH- or NR,o-; or one of the groups of the formulae (Va) - (Vc)

- 5 R18 0 o x! 11 0 X2 Rg R8 X1 X \X5 R30 (Va) o o n R15 (Co-R8)i - (R8CO) j- R1s - X:, N jX-R'15 -X -: N.; N R1s CO-R8) j-

N N NiN (Vb) - (Rg-CO);-R1s-X X-R1s-(CO-Rg) j-

- (Rg-CO)j-R1s R15 (Co-R8)i - (R8-CO) j- Rts - N.: N.:: N- R1s iCO-R28) j N < N

X- R1s iCO-R28) j- (Vc) when s is 6, A is C6-C,0alkanehexayl; C6-C, 2alkanehexsyl substituted by OH and/or interrupted by oxygen, -NH- or NR1o-; or one of the groups of the formulae (Via) - (Vlf) . . ,. R J X X2 Rg/ R3,::X6 X Xs R30 (Via) 0 / 0 O

Rl29

- 6 - (Rg-CO)j-R1s R1s tCO-R29)i - (R8-CO) j- R1s - N y N:: N - R,5 COR28) j N < N

(R30-CO)j-R'5-N-R,51CO-R3,)j- (Vlb) - (R8-CO) j- R1s R1s tco-R8)i-

- (R8-CO) j- R1s - N.:,N: X-R''5 -X: N y N R,s -tCO-R8)j-

N:,N N::N (Vlc) - (Rg-CO)j-R,5-X X-R1s-(CO-Rg) j-

R,5 (CO-R8)j - (R8-CO);- R1s - X:,N:'X-R' 5 -X:,: N. y N - R1s -tCO-R8)j-

N:,N N:N

- (Rg-CO)j-R1s X N-R1s-(CO-Rg) j- (Vld) R 5-(CO-Rg) j-

- (R8-Co) j R'5 R1s tCo-R8)i-

- (R8-CO):- R1s - N.:' N:'XR',5N R',5 X:: N. ^: N R1s -tCo-R8)i-

N.: N N ' N N:> N (Vle) zzN N;R1s tCO-R8);- Z R,5 tCo-R8) j

- 7 (R8-CO) j- R1s - X r,N:'X R',5 N Rt15 X:: N.:, X - R1s 1Co-R8)i-

N N N' N N.,N

l' (Vlf) - (R8-Co),- R,5 X X N X - R1s iCo-R8)i- X-R1 Co-R8)i-

R15 {CO-R8) j when s is 7, A is C7-C,Oalkaneheptayi; C7-C'2alkaneheptayl substituted by OH and/or interrupted by oxygen, -NH- or -NR,o-; or one of the groups of the formulae (Vlla) - (VlJd) - (R8 O0)'- R1s R,5 (co-R8)'-

(R8-C ) R1s - N:, N::X-R',5 -X: N.: N - a1s NCO-R8) j-

N:,N N:N

- (R9-cO)j-R15-x N\ R1s-(CO-Rg) j- (Vl la) R,5-(co-Rg) j-

-(R8-co), R,5 R,5 co-R8) \ / - (R8-CO), R1s - N. y N X-R,5 N-R',5 X; N, N - R1s iCO-R8) j-

NiN N N N;N (Vllb) Z Z N N - R1s iCO-R8);- X-R1s-(CO-R9) j-

R,5 tC -R8), -CO), R,s-X,N::X R',5 1 Rl,5 X:: Nt,X-R,siCO-R8)j-

N:N N ' N N. jN (Vllc) - (R8-co)j- R,5 x X N X - R's iCo-R8)i- N\R, CO-R8) j-

R,5 (co-R8) j R,5 (Co-R8)i

- 8 -(R8-CO) - Rls - X:, N:,X R'i lN Rl15 X N:, X - R1s iCO-R8)j NgN N' N N N -(R8-CO)j R15 X X N N R,5iCO-R8)j- X-R1 Co-R8)'- (Vlid) 1 R15 (CO-R8) j R15 tCO-R8), when s is 8, A is C8-C10alkaneoctayl; C8-C12alkaneoctayl substituted by OH and/or interrupted by oxygen, NH- or -NR,o-; or one of the groups of the formulae (Vlila) - (Vlilb) -(R8-CO), R,5 R 5 (coR8);-

(R8-CO),- R,5 - N. g, N: X-R',5 -X N -: N R s iCO-R8),-

N N N N

- (Rg-cO)j-R1s-N N-R1s-(CO-Rg)- (Vlila) - (Rg-CO)j-R15 R15-(CO-Rg)l-

- (R8-CO) j R15 R1s tCO-R8)i-

- (R8-CO), R1s - N y,N:4,XR 15 Ri15 X N N - R,5 iCO-R8)j NiN N N N N (Vlilb) - (R8-CO) j R15 Xz N N; R1s iCO-R8);- R1s-(CO-Rg),-

R15 (Co-R8)' the index i is zero or 1; R1, R2, R3 and R4, independently of each other, are C1-C4alkyl, or R1 and R2 or R3 and R4, together with the carbon atom to which they are bound, form a cyclopentyl or cyclohexyl ring; Rs is hydrogen; C1-C18alkyl; oxyl; OH; CH2CN; C1-C18alkoxy; C5C12cycloalkoxy; C3-C8alkenyl; C3-C8alkynyl; C7-C12phenylalkyl; C7C15phenylalkyi, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C1-C4alkyl and C1-C4alkoxy; C7-C15phenylalkoxy; C7 C15phenylalkoxy, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C1-C4alkyl and C1-C4alkoxy; or Rs is C1-C8alkanoyl; C3-Csalkenoyl; C1-C,8alkanoyloxy; glycidyl; or a group -CH2CH(OH)-G, in which G is hydrogen, methyl or phenyl; R8 and Rg, and R28, R29, R30, R31, R32 and R33, independently of each other, are C1-C4alkylene;

- 9 - R'o is C,-C8alkyl, C,-C8alkanoyl, C5-C,2cycloalkyl, C7-C, 5phenylalkyl which is unsubstituted or substituted on the phenyl ring by a radical selected from C,-C4alkyl and C,-C4alkoxy; or R'o is C,-C8alkyl or C,-C8alkanoyl substituted by OH, C,-C,2alkoxy and/or a residue benzophenonyl or benzophenonyloxy, wherein one or both phenyl rings of the benzophenone moiety are unsubstituted or substituted by OH, halogen, C,-C4alkyl and/or C,-C,8alkoxy; R., is C,-C,8alkyi; C2-C,8alkyl which is substituted by NH2, NHR,o, N(R,0)2, nitro, hydroxy and/or C,-C, alkoxy; C3-C,8alkenyl; Cs-C,2cycioalkyl; Cs-C,2cycloalkyl which is substituted by C,-C4alkyl and/or interrupted by -O-; R,2, R,3 and R,4, independently of each other, are C2-C,0alkylene; C3-C,zalkylene substituted by OH and/or interrupted by oxygen, phenylene, C,-C4alkylphenylene, -NH- or-NR,0-; C4C,2alkenylene; R,5 and Rt s, independently of each other, are is C2-C, 0alkylene; C3-C,2alkyiene substituted by OH and/or interrupted by oxygen, phenyiene, C,-C4alkylphenylene, -NH- or-NR,0-; R'6 is C3-C,Oalkantriyl; C3-C,2alkantrlyl substituted by OH and/or interrupted by oxygen, -NH or NR'o; R., is C4-C,Oalkantetryl; C4-C,2alkantetryl substituted by OH and/or interrupted by oxygen, NH- or -NR'o; R.8 is Cs-C,0alkanepentayl; C5-C,2alkanepentayi substituted by OH and/or interrupted by oxygen, -NHor-NR,0-; R,g is C6-C,0alkanehexayl; C6-C,2alkanehexayl substituted by OH and/or interrupted by oxygen, -NH- or-NR,o-; X is -O-, -NH- or -N(R'o); X1' X2' X3, X4, X5. X6, X7 and X8, independently of each other, are -Oor-NH-; . \0 4 Y is-O-ora residueof the formula NR 45 (CO-R g)'-N N Rs; / R, O R2 Z stands for halogen, NH2, NH R,o, N(R,0)2 or C, -C4alkoxy; Z. has one of the meanings given for Z or is -X-R'1s-XH and

- 1 0 N: NOUN Z2 is H or a residue of the formula 2 / l ) < Y R5 N N-(R gC) R 45 R3 0 R4 0 Where one compound carries more than one group denoted with the same symbol, these groups may be the same or different within their defined meanings.

Alkyiene, cycloalkylene or alkenylene residues may be bonded on different carbon atoms or on the same carbon atom thus embracing alkylidene, cycloalkylidene and alkenylidene, respectively. All residues, where appropriate, may be straight chain or branched unless otherwise indicated. Hetero atoms are non-carbon atoms, for instance N. O. S or P atoms.

Alkyl or alkylene interrupted by hetero groups such as oxygen or cycloalkylene may be interrupted by one or more of these groups as long as no linkages of the type 0-0, O-N etc. occur. The index s is the valency of A; for example, A as alkyl is a monovalent, A as alkylene a divaient, A as alkanetriyl a trivalent, A as alkanetetryl a tetravalent, A as alkanepentayl a pentavalent, A as alkanehexsyl a hexavalent, A as alkaneheptayl a heptavalent, and A as alkaneoctayl an octovalent saturated hydrocarbon residue. A residue which is interrupted is interrupted in a carbon-carbon single bond. A residue which is interrupted and/or substituted may be a residue interrupted in one or more carbon-carbon single bonds by one or more divalent interrupting groups, a residue substituted by one or more monovalent substituents, or a residue which is both interrupted in one or more carbon-carbon single bonds by one or more divalent interrupting groups and substituted by one or more monovalent substituents.

- 11 Thus, examples for A as C3-C,5alkylene substituted by one or more OH and/or interrupted by oxygen, phenylene, C,-C4alkylphenylene, -COO-, CONH-,-NH- or -NR,o- include groups of the formulae CH2CH(OH)CH2, CH2C(CH2OH)2-CH2, (CH2)2-N(CHO)-(CH2)2, (CH2)2-NH-(CH2)2, (CH2)2-o-(CH2)27 (CH2)2-o-(CH2)2-o-(CH2)2' CH2-CO-O-(CH2)2-O-(CH2)2-O-CO-CH2,CH2-CO-O-(CH2) 6-O-CO-CH2,

CH2-CO-O-(CH2)2-O-CO-CH2

Halogen is preferably chloro or bromo, especially chloro.

C6-C,2aryl is preferably phenyl or naphthyl, especially phenyl.

The compounds of the invention can be pure or mixtures of compounds.

R. R2, R3, R4 R5, R'o as alkyl are, within the definitions given, for example methyl, ethyl, propyl such as n- or isopropyl, butyl such as n-, iso-, sec- and tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexedecyl, heptadecyl or octadecyl.

R8, Rg, R,2, R,3, R14, R s, R',5 and R28 - R33 as alkylene are, within the definitions given, for example methylene, 1,2-ethylene, 1,1-ethylene, 1,3-propylene, 1,2-propylene, 1,1-propylene, 2,2-propylene, 1,4-butylene, 1,3-butylene, 1,2-butylene, 1,1-butylene, 2,2-butylene, 2,3-

butylene, or-CsH10-'-C6H,2-, C7H,4, -C8H16-, -CgH,8-, -C,oH20-, -C,,H22-, -C,2H24-, -C,3H26-, -

C,4H28-, -C1sH3o-, -C,6H32-, -C,7H34-, -C18H36-.

,. . R8, R. and R28 - R33 are especially preferred as methylene.

In R5, R'o, R11 as C5-C,2cycloalkyl or cycloalkoxy, the cycloalkyl part is, for example, cyciopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl or cyclododecyl. Cs-C,2-Cycloalkenyl includes cyclopentenyl, cyclohexenyl, cycloheptenyl, cyciooctenyl, cyclononenyl, cyclodecenyl, cycioundecenyl, cyclododecenyl.

- 12 C,-C4alkyl or akloxy substituted cycloalkyl or phenyl (containing mainly 1-3, e.g. 1 or 2 alkyl groups) include inter alla 2- or 4methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tbutylcyclohexyl, methylphenyl, methoxyphenyl, dimethylphenyl. Phenylalkyl or phenylalkoxy are alkyl or alkoxy each of which is substituted by phenyl.

R5, R'o as phenylalkyl or phenylalkoxy are, within the definitions given, for example benzyl, benzyloxy, a-methylbenzyl, a-methylbenzyloxy, cumyl, cumyloxy.

R5 and Rio as alkanoyl are, for example, formyl, acetyi, propionyl, butyryl, pentanoyl, octanoyl; Rs as alkanoyi is preferred as C2C8alkanoyl, especially acetyl.

Residues alkenoyl, such as in the definition of Rs, are most preferably acryloyl or methacryloyl. Residues alkenyl, such as in the definition of Rs, are most preferably allyl.

X is preferably NH; X,-X6 are most preferably O; Z is most preferred as N(R'0)2; i is most preferred as zero.

The index p is preferably from the range 2-6.

A preferred blend of polycarbonate with acrylonitrile-butadiene-styrene terpolymer (component (A) of the above composition) is a blend of 10 to 90 parts by weight of !. _. polycarbonate with 90 to 10 parts by weight of acrylonitrile-butadiene-styrene terpolymer.

Polycarbonates contained in these blends are to be understood as being especially those polymers the constitutional repeating unit of which corresponds to the formula O, wherein W is a divalent phenolic radical. Examples of TO-w-o: W are given inter aiia in US-A 960863 and DE-A3922496. W can be derived, for example, from hydroquinone, resorcinol, dihydroxybiphenylene or bisphenols in the broadest sense of

- 1 3 the term, such as bis(hydroxyphenyl)alkanes, cycloaikanes, sulfides, ethers, ketones, sulfones, sulfoxides,, '-bis(hydroxyphenyl) diisopropylbenzenes, for example the compounds 2,2-bis(4-hydroxyphenyl) propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)-

propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5dibromo-4-hydroxy-

phenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, or from the bisphenols of the formulae OH CH CH3 CH3

O _j: 0 04 = 0 O O O '_\ O

CH3 CH3 CH CH3

CH3

- 14 O: < O O: -O

CH CH3 CH3 CH

CH2-C(CH3)3

O O O O

The composition of the invention preferably contains as further component (C) a UV absorber from the class of the benzotriazoles, o-hydroxyphenyl-striazines and/or benzophenones, examples of which are listed below..

Preferred is composition, wherein in the compound of formula I (component B) s is from the range 2 to 6; when sis2 A is C2-C,Oalkylene; C3-C, 2alkylene substituted by OH and/or interrupted by oxygen, -NH- or NR,o-; or a group of the formula -R -COO-R,2-OCO-Rg- (lla); .. when s is 3, A is a group of the formula (Illa) Rl3 (Illa) O O

RELAX, R,5 R'-X>R/

when s is 4, A is one of the groups of the formulae (IVa) or (IVd)

- 1 5 Rl8Wo xl R/:X 17 X2 Rg/ (IVa) 1 4 Rl29 - (Rg-CO)'-R1s R15 (CO-R28)i -(R8-CO) j- R1 s N:' N.:: N - R1s 1CO-R28) j N: N z (IVd) when s is 5, A is a group of the formula (Va) R|80 o O X3 X24Rg/ RJ:X, X \Xs R30: (Va) /40 R29 when s is 6, A is one of the groups of the formulae (Vlb) - (Vl

- 16 -(Rg-CO)j-R,5 R15(C -R29)l - (R8-CO)j- R1s - N: N:N- R1s 1CO-R28)j N N (R30-CO) j-R'5-N-R,5 CO-R3,)j- (Vlb) -(R8-CO)j- R,5 R,5 (co-R8) j - (R8Co)j- R1s - N y N:rX-R''5 -X f: N. r N - R1s iCO-R8)j-

N N N N (Vlc) -(Rg-CO)j-R1s-X X-R1s-(CO-Rg)-

R,5 CO-R8) j - (R8-CO)j- R1s - X:r N X-R',5 -X: N y N - R,5 iCO-R8); N N N N

-(Rg-CO)j-R1s-X N-R1s-(CO-Rg)j- (Vld) R,5-(CO-Rg)j-

- (R8-CO) j R15 R,5 co-R8)j -(R8-CO)j- R1s - N r N.:,X-R',5 1 R',5 X:, N. ^: N - R1s iCO^R8);-

N. iN N N N. N (Vle) Z z N N - R,siCO-R8);- z R,5(C -R8)j-

- 1 7 - (R8-CO). R1s - X r N i,X-R',5 <: R.'5 X:; N>r X - R1s tCO-R8),-

N:N N N NiN (Vlfl -(R8-Co)j. R,5-X X N X - R,s tCO-R8)' X-R, CO-R8)j-

R15 tCo-R8), the index i is zero or 1; R., R2, R3 and R4, independently of each other, are methyl; Rs is hydrogen; C, -C,8alkyl; oxyl; OH; C, -C, 8alkoxy; C5-C,2cycloalkoxy; C3-C8alkenyl; or Rs is C,-C8alkanoyl; C3C5alkenoyl; C,-C'8alkanoyloxy; glycidyl; or a group -CH2CH(OH)-G, in which G is hydrogen, methyl or phenyl; R8 and R., and R28, R29, R30, R31, R32 and R33, independently of each other, are methylene; R'o is C,- C8alkyl, C,-C8alkanoyl, C5-C,2cycloaikyl; R12 is C2-C,0alkylene; or C3-C, 2alkylene interrupted by oxygen, -NH- or-NR10-; R,5 and R',5, independently of each other, are is C2-C,0alkylene; R 7 is C4-C, Oalkantetryl; R18 is Cs-C10alkanepentayl; X is -O-, -NH- or -N(R10)-; X1, X2, X3, X4, X5, X6, X7 and X8, independently of each other, are -O- or-NH- ; and Z stands for NHR10, N(R10)2 or C1-C4alkoxy.

Many compounds of the above component B are novel. The invention therefore also relates to a compound of the formula (I') or (II) R R - O - A (I)

- 18 Z - /N\ X R' 5 X

N: N (II)

l R O P wherein p is from the range 1-10; s is from the range 1 to 8, preferably 2 to 8; R., R2, R3 and R4, independently of each other, are C,C4alkyl; R5 is hydrogen; C,-C,8alkyl; oxyl; OH; CH2CN; C,-C,8alkoxy; C5-C, 2cycloalkoxy; C3-C8alkenyl; C3-C8alkynyl; C,-C,2phenylaikyl; C7C15phenylaikyl, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C1-C4alkyl and C1-C4alkoxy; C,-C15phenylalkoxy; C, C,5phenylalkoxy, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C1 -C4alkyl and C, -C4alkoxy; or Rs is C, C8alkanoyl; C3-Csalkenoyl; C1 -C18alkanoyloxy; glycidyl; or a group CH2CH(OH)-G, in which G is hydrogen, methyl or phenyl; when s is 1, A is C2-C,8alkylene substituted by OR30, wherein R30 is C1-CRalkyl or C1 C8alkanoyl substituted by a residue benzophenonyl or benzophenonyloxy, wherein one or both phenyl rings of the benzophenone moiety are unsubstituted or substituted by OH, halogen, C,-C4alkyl and/or C,C18alkoxy; when s is 2 : A is C3-C,5alkylene substituted by one or more OH and/or interrupted by one or more oxygen, x N X phenylene, C1C4alkylphenylene, -COO-, -CONH-, N:, N N --- N; N, -NH- and/or -NR,o-; or A is C4-C12alkenylene; z N 1Z

- 1 9 and when Rs is not hydrogen, A also embraces C2-C'0alkylene; C2-C, 0alkylene interrupted by phenylene or C1-C4alkylphenylene; when s is 3, A is C3-C,Oalkantriyl; C3-C,2alkantriyl substituted by OH and/or interrupted by oxygen, -NH- or -NR,o-; or one of the groups of the formulae (Illa) (Ilid) RIB O (Ilia) O O RJ:X, R15 RI' XJ:Rg/ - (R6-CO). R's-X -: N:rXRis iCO-R28) NiN (Illb) - (Rg-CO)j-Ris-X - (Rg-cO)j-Ris - (Ra-CO). R,s N:, N:X- R's iCO-R26) j N N z (IIIC) ' R28 0

(Ilid) X R '<x 16'X2J(R / when s is 4, A is C4-C,Oalkantetryl; C4-C, 2alkantetryl substituted by OH and/or interrupted by oxygen, -NH or -NR,o; or one of the groups of the formulae (IVa) - (IVd)

- 20 Rl8:O X O ' O

R J:x i X2 Rg/ X4 (IVa) R /(O -(R8-CO) j- R1s Xy'N: X-R',5 -X:: N yX - R, 5iCO-R8);-

N N N N (IVb) - (Rg-CO)j-R1s-X X-R1s-(CO-Rg);-

- (Rg-CO)j-R1s - (R8-CO) j- R1s - N:, N 4:X- R1s iCO-R28)j N < N

(.,,., l -- X-R1s co-R28)j- (IVc) -(Rg-CO)j-R,5 R. co-R2)-

- (R8-CO) j- R1s - N.:, N.:, N R1s CO-R28) j N i N z (IVd) when s is 5, A is C5-C'Oalkanepentayi; C5-C,2alkanepentayl substituted by OH and/or interrupted by oxygen, -NH- or -NR,o-; or one of the groups of the formulae (Va) - (Vc)

- 21 X2 Rg/ R8 X, I \X R. (Va) o o D 1'29 R15 (CO-R8)i-

-(R8-CO) j- R1s-X 'N:4,X-R'15-X r N rN -R1sico-R8)i N N N:N (Vb) - (Rg-cO) j-R1s-X X-R1s-(CO-Rg) I-

- (Rg-CO);-R1s R15 (Co-R8)l - (R8-CO) j- R1s N:, N.:rN- R1siCO-R28)j N;, N - X- R1s iCO-R28) j- (VC) when s is 6, A is C6-C10alkanehexsyl; C6-C, 2alkanehexayl substituted by OH and/or interrupted by oxygen, -NH- or -NR, o-; or one of the groups of the formulae (Via) - (Vlp J:X X X R/

R3,: X6 Xs::R30 (Via) D 1 219

- 22 - (Rg-CO);-R1s R15 tCo-R29)i (R8-CO) j- Rls - N y N, N- R1s 1CO-R28) j N < N

(R30-CO) j-R,5-N-R,5 1CO-R3,)j- (Vlb) - (R8-CO) j- R1s R1s (CO-R8) j-

- (R8-CO) j- R1s - N r, N.:,X-R',5 -X-; N. y N - R1s CO-R8) j-

NiN N:N (Vic) - (Rg-CO);-R1s-X X-R1s-(CO-Rg) j-

R,5 {Co-R8)i - (R8-CO) j- R1s - X r N. X-R',5 -X:: N. y N R1s CO-R8)j-

N:N N N

- (Rg-CO)j-R1s-X N-R1s-(CO-Rg) j- (Vld) R,5-(CO-R9) j-

- (R8-CO) -j R15 R15 tCO-R8)j - (R8-CO) j- R1s - N. y,N:,XR 15 1 R',5 X:, N.: N - R1s 1C -R8) j-

NiN N ' N N. N (Vle) zZ N N; R1s -tCo-R8)i- Z R15 tCo-R8)i

- 23 -(R8-CO)j R1s-XyN:'X R'15 1 Rt1s X:;N:X R1sico-R8)i-

N:N N N N. iN (Vlf) - (R8-CO)j- R15-X X N X - R,5 1Co-R8)i X-R1 Co-R8) R15 (CO-R8) j when s is 7, A is C7-C10alkaneheptayl; C7-C12aikaneheptayl substituted by OH and/or interrupted by oxygen, -NH- or -NR10-; or one of the groups of the formulae (Vlla) - (Vlid) - (R8-CO) j- R1s R15 IC Ra)j (R8-CO) j- R1s - N.:',N rX-R'15 -X:r N:, N - R1s iCO-R8)j N:N NiN - (RgCO)j-R1s-X N-R1s-(CO-Rg) j- (Vl la) Rls-(CO-Rg) j-

- (R8-CO) j R15 R,5 CO-R8)j-

-(R8-CO) j R's N.:,N:X R 15 Re15 X N. y N - R,5 1Co-R8)i N:N N N NiN (Vllb) Zl'N Nj R1s 1CO-R8); X-R1s-(CO-Rg) j-

R15 (CO-R8) j - (R8-CO) j- R1s - X y'N:,X R,5 Re,5 X: N. y X - R1s 1Co-R8) i-

N N N N N:N (VIIC)

-(R8-CO)j R15 X X N X-R'siCo-R8)i- N\R1 Co-R8)i R15 (Co-R8) j R15 (CO-R8) j

- 24 - (R8-CO) j- R1s - X: N::X R',5 1 R'15 X:; N: X - R1s -tCO-R8) j-

N,N N' N N:>N

-(Ra-cO); R 5 X X N N-R,5iCO-R)- X-R, Co-R8)i- (Vlid) | R,5 tC -Ra)' R,5 (C -R8)

when s is 8, A is C8-C,0alkaneoctayl; C8-C,2alkaneoctayl substituted by OH and/or interrupted by oxygen, NH- or -NR,o-; or one of the groups of the formulae (Vlila) - (Vlilb) - (R8-co).' R,5 R,5 (co-R8)j-

- tR8-CO)'. R,s - N.:',N:'X-R',5 -X:: N. ' N - R,s iCo-R3)'-

N:,N N:N

- (R9-CO)j-R s-N N-R,s-(CO-Rg).- (Vlila) - (R9-CO)'-R,5 R,5-(co-Rg);-

-(R8-CO) j R1s R1s tCO-R8)j-

\ /

- (R8-CO) j- R1s - N.: N:'X R' s g Rt1s X:: N r N - R1s tCo-R8)i-

N:,N 1 N N (Vlilb) -(R8-co) i R,s-X z N N - R4s tCo-R8)i- R,s-(CO-Rg)'-

R,5 tC -R8) the index i is zero or 1; R8 and Rg, and R28, R29, R30, R3,, R32 and R33, independently of each other, are methylene, and when Rs is not hydrogen, additionally embrace ethylene; R,o is C,-C8aikyl, C1C8alkanoyl, Cs-C,2cycloalkyl, C7-C,sphenylalkyl which is unsubstituted or substituted on the phenyl ring by a radical selected from C,-C4alkyl and C,-C4alkoxy; R,2, R,3 and R,4, independently of each other, are C2-C, 0alkylene; C3-C,2alkyiene substituted by OH and/or interrupted by oxygen, phenylene, C,-C4alkylphenylene, -NH- or -NR,o-; C4-C,2alkenylene; R1s and R',5, independently of each other, are is C2-C,0alkylene; C3-C,2alkylene substituted by OH and/or interrupted by oxygen, phenylene, C,C4alkylphenylene, -NH- or -NR,o-;

- 25 R.6 is C3-C,Oalkantrlyl; C3-C,2alkantrlyl substituted by OH and/or interrupted by oxygen, -NH or -NR'o; R,7 is C4-C,Oalkantetryl; C4-C, 2alkantetryl substituted by OH and/or interrupted by oxygen, NH- or -NR10; Rue is Cs-C10alkanepentayl; Cs-C,2alkanepentayl substituted by OH and/or interrupted by oxygen, -NH- or-NR,0-; R,g is CB-C,0alkanehexayl; C6-C,2alkanehexayl substituted by OH and/or interrupted by oxygen, -NHor-NR,0-; X is -O-, -NH- or-N(R,0)-; X1' X2, X3, X4, X5, X6, independently of each other, are -O- or-NH-; 0 4 Y is -O- or a residue of the formula N R 45 (CO-R g)'-N N R; O R2 Z stands for halogen, NH2, NHR10, N(R10)2 or C1-C4alkoxy; Z1 has one of the meanings given for Z or is -X- R'1s-XH and INNS NOON Z2 is H or a residue of the formula ' / R5 N N-(R gC) R 5 R3 O R4 O Preferred meanings in the formula (1') include those given above for formula (1), where appropriate. Also preferred is a compound of the formula (1') or (11) wherein p is from the range 2-6, s is from the range 2 to 8; R1, R2, R3 and R4, independently of each other, are methyl or ethyl;

- 26 Rs is hydrcgen; C1-C18alkyl; oxyl; OH; CH2CN; C1-C18alkoxy; Cs-C, 2cycloalkoxy; c3-c8alkenyl; C7-C,2phenylalkyi; C7-C,5phenylalkoxy; or R5 is C,-C8alkanoyl; C3-C5alkenoyl; C, C18alkanoyloxy; glycidyl; or a group CH2CH(OH)-G, in which G is hydrogen, methyl or phenyl; when s is 2 A is C3-C12alkylene substituted by OH and/or interrupted by oxygen, -NH- orNR10-; C4-C12alkenylene; or one of the groups of the formulae (lla) (lle) -R8-COO-R12-OCO-Rg-; -R8-CONH-R13-NHCO-Rg-; -R8-COO-R14-NHCO-Rg-; (lla) (lib) (llc) - (R8-CO) j- R15-X y,N:'Z N. N (i Id) - (R9-CO)j-R,s - X - (Rg-CO)j-R1s -(R8-CO)j-Ris-NyN j z NiN (lie) z and when Rsis not hydrogen, A also embraces C2-C10alkylene; C2-C10alkylene interrupted by phenylene or C1-C4alkylphenylene; when s is 3, A is C3-C10alkantriyl; or one of the groups of the formulae (Illa) - (Ilid) Rl8;o (Illa) R X1 R15R'15 X2 Rg/

- 27 - (R8-CO) j- R1s-X y N. j:X- R1s CO- 8) j N N (Illb) - (Rg-CO)j-R1sX - (Rg-CO);-R1s - (R8-CO) j- R1s - N. y N. j'X- R1s iCO-R28) j N N z (Illc) Rl8 jo (Illd) y A RJ X 16 X2 R/

when s is 4, A is C4-C,Oalkantetryl; or one of the groups of the formulae (IVa) - (IVd) ( Rl8f o X R/ X- 17 X2 Rs/ (IVa) / 0 R. 129

- (R8-CO) j- R1s X r N. X-R',5 -X: N , X - R1s iCO-R8) j-

N N N:N (IVb) - (R8-CO)j-R1s-X X-R1s-(CO-Rg) j-

- 28 - (Rg-CO)j-R1s - (R8-CO) j- R1s - N. r N.:rX R1s iCO-R28) j N < N

X- R,5 CO-R28)j- (IVC) - (Rg-CO);-R.; R15 (Co-R2B)i - (R8-CO) j- R1s - N N:N- R1s CO-R28)j N N Z (IVd) when s is 5, A is Cs-C,Oalkanepentayl; or a group of the formula (Va) O X, O: (Va) R/:O when s is 6, A is C6C10alkanehexayl; or one of the groups of the formulae (Vlb) - (Vlf) - (RgCO)j-R.; R4s (CO-R29)j - (R8-CO) j- R1s - N:, N:rN- R1s iCO-R28) j N N (R30-Co) j-R,5-N-R1s iCO-R3,) j- (Vl b)

- 29 -(R8-CO) j- R1s R15 tCO-R8)i - (R8-CO) j- R1s - N.:,,N X-R'15 -X: N y N R15 tCO-R8)j N:N NiN (Vlc) - (Rg-cO)j-R15-X X-R1s-(CO-Rg)i-

R1s tco-R8)i -(R8-CO) j- R15-X: N. X-R'1s-X:: N y N -R1s tCO-R8)j NiN N:N - (Rg-CO)j-R1s-X N-R1s-(CO-Rg) j- (Vld) R15-(CO-Rg) j-

-(R8-CO)-j R15 R15 (CO-R8)j - (R8-CO) j- R15 - N. y'N 'XR 15 Re15 X: N y N - R151C -R8)j-

N N N N N N (Vle) ZZ N Nj R1s 1Co-R8)i Z R15 (CO-R8) j - (R8-CO) j- R1s X:,N:rX R 15 Re15 X: N yX R1s tCo-R8)i-

N:N N N N N (Vlfl -(R8-Co)i R1s-X X N X-R1s1Co-R8)i X-R1 Co-R8)' R15 (CoR8) j when s is 7, A is C7-C10alkaneheptayl; when s is 8,

- 30 A is C8-C,0alkaneoctayl; or one of the groups of the formulae (Vlila) - (Vlilb); the index i is zero or 1; R8 and Rg, and R28, R29, R30, R3,, R32 and R33, independently of each other, are methylene; Rio is C,C8alkyl, C,-C8alkanoyl, C5-C,2cycloalkyl, C7-C1sphenylalkyl; R,2, R,3 and R,4, independently of each other, are C2-C,0alkylene; C3-C,2alkylene substituted by OH and/or interrupted by oxygen, -NH- or-NR,0-; C4-C, 2alkenylene; R,s and R',5, independently of each other, are is C2-C, 0alkylene; C3-C,2alkylene substituted by OH and/or interrupted by oxygen, phenylene, C,-C4alkyiphenylene, -NH- or -NR,o-; R.6 is C3-C'Oalkantriyl; R,7 is C4-C,Oalkantetryl; R.8 is Cs-C,Oalkanepentayl; X is -O-, -NH- orN(R,0)-; X,, X2, X3, X4, Xs, independently of each other, are -O- or-NH-; and Z stands for halogen, N H2, NH R,o, N(R,0)2 or C, -C4alkoxy.

Especially preferred is a compound of the formula (I') wherein s is from the range 2 to 6; R., R2, R3 and R4, independently of each other, are methyl or ethyl; Rs is hydrogen; C,-C,8alkyl; oxyl; OH; CH2CN; C,-C, 8alkoxy; Cs-C,2cycloalkoxy; C3-C8aikenyl; C7-C,2phenylalkyl; C7-C, sphenylalkoxy; or Rs is C,-C8alkanoyl; C3-Csalkenoyl; C, C,8alkanoyloxy; glycidyi; or a group -CH2CH(OH)-G, in which G is hydrogen, methyl or phenyl; when s is 2 A is C3-C,2alkylene substituted by OH and/or interrupted by oxygen, -NH- or-NR,0-; C4-C,2alkenylene; or a group of the formula (lie) -R -COO-R,2-OCO-Rg-; (lla) and when Rs is not hydrogen, A also embraces C2-C,0alkylene; when s is 3, A is C3-C,Oaikantriyl; or one of the groups of the formulae (Illa), (Illb) or (Ilid); when s is 4, A is C4-C,Oalkantetryl; or one of the groups of the formulae (IVa), (IVb) or (IVd);

- 31 when s Is 5, A is Cs-C,0alkanepentayi; when s is 6, A is one of thegroups of the formulae (Vlb) - (Vlf); the index i is zero or 1; Ra and Rg, and R2a, R29, R30, R31, R32 and R33, independently of each other, are methylene; R10 is Cl-Caalkyl, C'-Caalkanoyl, C5-C12cycloalkyl; R.2 is C2C,Oalkylene; C3-C,2alkylene substituted by OH and/or interrupted by oxygen, -NH- or -ORE-;

R's and R',5, independently of each other, are is C2-C,0alkylene; R,6 is C3-C,Oalkantrlyi; R,7 is C4-C,Oalkantetryl; X is -O-, -NH- or-N(R,0)-; X,, X2, X3, X4, independently of each other, are -O- or-NH-; and Z stands for NHR,o or N(R,0)2.

Most preferred is a compound of the formula (I') wherein s is 2, 3, 4 or 6; R., R2, R3 and R4 are methyl; Rs is hydrogen; C,-Caalkyl; C,-C,aalkoxy; cyclohexyloxy; allyl; benzyl; acetyl; C3-C4alkenoyl; glycidyl; when s is 2 A is C3-C,0alkylene substituted by OH or interrupted by oxygen, -NH- orNR,0-; or a group of the formula -Ra-COO-R,2-OCO-Rg- (lla); and when R5 is not hydrogen, A also embraces C2-C,0alkylene; when s is 3, A is a group of the formula (Illa); when s is 4, A is a group of the formula (IVa) or (IVd); when s is 6, A is a groups of the formula (Vle); the index i is zero; Ra and Rg, and R2a, R29, R30, R3,, R32 and R33 are methylene; R'o is C,-Caalkyl, formyl, acetyl, or cyciohexyl; R 2 is C2-C, 0alkylene; or C3-C,0alkylene interrupted by oxygen; R,5 and R''5, independently of each other, are is C2-C10alkylene; R,7 is C4- C10alkantetryl;

- 32 X is -NH-; Xl,X2,X3,X4are-O-;and Z stands for N(R'0)2.

The preparation of compounds of the formula I or 1' can start from the compound 3,3,5,5-

tetrealkyl-piperazin-2,6-dione and can follow or be carried out in analogy to methods described in the documents cited on page 1 or standard procedures described in textbooks of organic chemistry; examples for such methods are alkylation, (trans)esterification or etherification, substitution etc. Compounds thus obtained may be further derivatized by applying suitable synthetic methods known in the art, e.g. in analogy to methods described in EP-A-375612, US-A-5204473, US-

A-5004770, and Kurumada et al., J. Polym. Sci., Poly. Chem. Ed. 23, 1477 (1985), as well as US-5449776, example 8, and publications cited therein, for the modification of piperidine derivatives. The novel compounds of present invention can be employed with advantage for stabilizing organic material against the damaging effect of light, oxygen and/or heat. They are notable for high substrate compatibility and good persistence in the substrate. Examples of materials to be stabilized in accordance with the invention are: 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, po-

lybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HOPE), high density and high mole-

cular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight poly-

ethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LOPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

r - 33 Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, prefe-

rably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods: a) radical polymerization (normally under high pressure and at elevated temperature).

b) catalytic polymerization using a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or Vlil of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either - or c-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(l11) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalysts can be used by themselves in the polymerization or further activators may be used, typically metal alkyls, metal hydrides, metal aikyl halides, metal alkyd oxides or metal alkyloxanes, said metals being elements of groups la, Ha and/or Illa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyi ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

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

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutyiene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copo-

lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octane copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethy-

lene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl ace-

tate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copo

- 34 Iymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexediene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EM), LLDPE/EVA, LLDPE/EM and alter-

nating or random polyalkyiene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

4. Hydrocarbon resins (for example Cs-Cg) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkyienes and starch.

5. Polystyrene, poly(p-methyistyrene), poly(cc-methylstyrene).

6. Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acryloni-

trlie/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpo-

lymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/iso-

prene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/ styrene.

7. Graft copolymers of styrene or cc-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadieneacrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl meth-

acrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylo-

nitrile and maleic andydride or maleimide on polybutadiene; styrene and maleimide on poly-

butadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acry-

lonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acry-

lates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.

- 35 8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo-

chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogencontaining vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from c, -unsaturated acids and derivatives thereof such as polyacry-

lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni-

triles, impact-modified with butyl acrylate.

10. Copolymers of the monomers mentioned under 9) with each other or with other unsatu-

rated monomers, for example acrylonitrlie/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acry-

lonitrile/ alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or ace-

tals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethy-

lene oxide, polypropylene oxide or copolymers thereof with bisqlycidyl ethers.

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

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

- 36 15. Polyurethanes derived from hydroxyi-terminated polyethers, polyesters or polybutadi-

enes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from mxylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isopUthalic or/and terephthalic acid and with or without an ela-

stomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-

m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).

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

18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4dimethylolcyclohexane tereptthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also poly-

esters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

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

sins and melamine/formaldehyde resins.

- 37 22. Drying and non-drying alkyd resins.

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

24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acry-

lates, urethane acrylates or polyester acrylates.

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

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F. which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators. 27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives. 28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Poly-

amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermopiastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

The invention therefore also provides compositions comprising A) an organic material which is sensitive to oxidative, thermal and/or actinic degradation, and

- 38 B) at least one compound of the formula 1', and provides for the use of compounds of the formula 1' for stabilizing organic material against oxidative, thermal or actinic degradation. Effects of degradation inter alla may be discoloration, molecular breakdown or buildup.

Thus, the invention likewise embraces a method of stabilizing organic material against thermal, oxidative and/or actinic breakdown/buildup, which comprises applying or adding at least one compound of the formula 1' to this material.

In general, the compounds of the formula I or 1' are added to the material to be l, - t stabilized in amounts of from 0.1 to 10 %, preferably from 0.01 to 5 %, in particular -A -A from 0.01 to 2 % (based on the material to be stabilized). Particular preference is given to the use of the novel compounds in amounts of from 0.05 to 1.5 %, especially from 0.1 to 0.5 %.

In addition to the compounds of the formula I or 1', the novel compositions may as additional component C comprise one or more conventional additives such as, for example, those indicated below.

1. Antioxidant_ 1.1. Alkylated mono ?henols, for example 2,6-di-tertbutyl-4-methylphenol, 2-tert-butyl-4,6-di-

methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-nbutylphenol, 2,6-di-tert-bu-

tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methyiphenol, 2-(amethylcyclohexyl)-4,6-dimethyl i... phenol, 2,6-dioctadecyl-4methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-

methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'methylundec-1'-yl)phenol, 2,4-di-

methyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec1'-yl)phenol and mixtures thereof.

1.2. AikylthiomethvlPhenols, for example 2,4-dioctylthiomethyl-6-tertbutylphenol, 2,4-dioc-

tylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-

4-nonylphenol.

- 39 1.3. Hvdroquinones and alkvlated hydroquinones, for example 2,6-ditert-butyl-4-methoxy-

phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6diphenyl-4-octade-

cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl4hydroxyanisole, 3,5-di-tert-

butyl4-hydroxyanisole, 3,5-di-tert-butyl4-hydroxyphenyl stearate, bis-(3, 5-di-tert-butyl4-

*hydroxyphenyl) adipate.

1.4. Tocopherols, for example a-tocopherol, p-tocopherol, y-tocopherol, btocopherol and mixtures thereof (Vitamin E).

1.5. Hvdroxvlated thiodiphenyl ethers, for example 2,2'-thiobis(6-tertbutyi-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tertbutyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-

methylphenol), 4,4'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis(2,6dimethyl-4-hydroxyphe-

nyi)disulfide. 1.6. Alkylidenebisphenols, for example 2,2'-methylenebis(6tert-butyl4-methylphenol), 2,2'-

methylenebis(6-tert-butyl4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(amethylcyclohexyl)-

phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'methylenebis(6-nonyl-4-me-

thylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'ethylidenebis(4,6-di-tert-butyl-

phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'methyienebis[6-(oc-methylben-

zyl)-4-nonylphenol], 2,2'-methyienebis[6-(a,c -dimethylbenzyl)-4nonylphenol], 4,4'-methy-

lenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2methylphenol), 1,1-bis(5-tert-

butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2hydroxybenzyl)4-

methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1, 1-bis(5-tert-butyl-4-

hydroxy-2-methyi-phenyi)-3-n-dodecylmercaptobutane, ethylene glycol bis[3, 3-bis(3'-tert-

butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl4-hydroxy-5-methylphenyl)dicyclopentadi-

ene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis-(3,5-di-tert-butyl-4-hydroxyphe-

nyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)4-ndodecylmercaptobutane, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2methylphenyl)pentane. 1.7. O-, N- and S-benzvl compounds, for example 3,5, 3',5'-tetra-tert-butyl-4,4'-dihydroxydi-

benzyl ether, octadecyl4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl4-hydroxy-

3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl4hydroxybenzyl)amine, bis(4

- 40 tert-butyl-3-hydroxy-2,6-dimethyibenzyl)dithioterephthalate, bis(3,5di-tert-butyl-4-hydroxy-

benzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxvbenzylated nnalonates, for example dioctadecyl-2,2-bis-(3,5di-tert-butyl-2-hy-

droxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5methylbenzyl)-malonate, di-

dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1, 1,3,3-te-

tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyi)malonate. 1.9. Aromatic hvdroxybenzvl com ounds, for example 1,3,5-tris-(3,5-ditert-butyl4-hydroxy-

benzyi)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetrame-

thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1. 10. Triazine Compounds, for example 2,4-bis(octylmercapto)-6-(3,5-ditert-butyl-4-hy-

droxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4hydroxyanilino)-1,3,5-

triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl4-hydroxyphenoxy)-1,3, 5-triazine, 2,4,6-

tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris-(3,5di-tert-butyl4-hydroxy-

benzyl)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)-hexabydro-1,3,5-triazine, 1,3, 5-tris(3,5dicyclohexyl-4-hydroxyben zyl)isocyanurate. 1.11. Benzviphosphonates, for example dimethyl-2,5-di-tert-butyl4-hydroxybenzyiphospho-

nate, diethyl-3,5-di-tert-butyl4-hydroxybenzylphosphonate, dioctadecyl3,5di-tert-butyl-4-hy-

droxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. AcylaminoPhenols, for example 4-hydroxylauranilide, 4hydroxystearanilide, octyl N-

(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate. 1.13. Esters of B-(3,5-ditert-butyl4-hvdroxYphenyi)prouionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-

nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy-

lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hy

-41 droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol-

propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of Q-(5-tert-butYI -hydroxy-3-methvlphenYl)propionic acid with mono- or poly-

hydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexane-

diol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-

bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7trioxabicyclo[2.2.2]octane.

1.15. Esters of Q-(3,5-dicYclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentserythritol, tris(hydroxyethyl)isocyanurate, N,N'bis(hydroxyethyl)ox-

amide, 3-thiaundecanoi, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy-

droxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenvl acetic acid with monoor polyhydric alco-

hols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyi glycol, thiodiethylene glycol, diethylene glycol, , triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox-

arnide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy-

droxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of,B-(3,5-di-tert-butvl-4-hYdroxYphenYI)proPionic acid e.g. N,N'-bis(3,5-di-tert-

butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tertbutyl-4-hydroxy: phenylpropionyl)trimethylenediamide, N,N'-bis(3,5-ditert-butyl -hydroxyphenylpropionyl)-

hydrazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy) ethyl]oxamide (Naugard XL-1 supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

- 42 1.19. Aminic antioxidants, for example N,N'-di-isopropyl-pphenylenediamine, N,N'-di-sec-

butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N. N'-bis( 1-

ethyl-3-methylpentyi)-p-phenylenediamine, N. N'-bis(1 -methylheptyl)-pphenylenediamine, N. N'-dicyclohexyl-p-phenyienediamine, N. N'-diphenyl-pphenylenediamine, N. N'-bis(2-naph-

thyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-( 1, 3-dimethyibutyl)-

N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-pphenylenediamine, N-cyclo-

hexyl-N'-phenyl-p-phenlenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N, N'-dimethyl-

N,N'-di-sec-butyl-p-phenyienediamine, diphenylamine, N-allyidiphenylamine, 4-isopropoxy-

diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octyiphenyl)-1napUthylamine, N-phe-

nyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tertoctyidiphenylamine, 4-

n-butylaminophenol, 4-butyrylaminophenoi, 4-nonanoylaminophenol, 4dodecanoylamino-

phenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tertbutyi-4-dime-

thylaminomethylphenol, 2,4'-d iam inodiphenyl methane, 4,4'-d iaminod iphenyl methane, N. N. N', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1, 2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl) biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-

octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-

octyidiphenylamines, a mixture of mono- and dialkylated nonyidiphenylamines, a mixture of mono- and dialkylated dodecyidiphenylamines, a mixture of mono- and dialkylated isopro-

pyl/isohexyidiphenylamines, a mixture of mono- und dialkylated tertbutyidiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzathiazine, phenothiazine, a mixture of mono- und dial-

kylated tert-butyl/tert-octylphenothiazines, a mixture of mono- und dialkylated tert-octyl-phe-

nothiazines, N-allylphenothiazin, N,N,N',N'-tetraphenyl-1,4-diaminobut-2ene, N,N-bis-

(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine, bis(2,2,6,6tetramethylpiperid-4-yi)-

sebacate, 2,2,6,6-tetramethylpiperidin--one, 2,2,6,6-tetramethylpiperidin4-ol.

2. UV absorbers and light stabilisers 2.1. 2-(2'-Hvdroxyphenvl) benzotriazoles, for example 2-(2'-hydroxy-5'-methylphenyl)-benzo-

triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'tert-butyl-2'-hydroxyphe-

nyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl) benzotriazole, 2-(3',5'-di-

tert-butyi-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl- 2'hydroxy-5'-methylphe-

nyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'hydroxyphenyl)benzotriazole, 2-(2'-

hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'hydroxyphenyl)benzotriazole,

- 43 2-(3',5'-bis-(a,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2(3'-tert-butyl-2'-hydroxy-

5'-(2-octyloxycarbonylethyl)phenyi)-5-chloro-benzOtriazole, 2-(3'-tertbutyl-5'-[2-(2-

ethylhexylOxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2(3'-tert-butyl-2'-hy-

droxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'tert-butyl-2'-hydroxy-

5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'hydroxy-5'-(2-octyloxy-

carbonylethyi)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2ethylhexyloxy)carbonylethyl]-2'-

hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2-(3'-

tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis-

[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-yiphenol]; the transesterification product of 2-

[3'-tert-butyl-5'-(2-methOxycarbonylethyl)-2'-hydroxyphenyl]-2Hbenzotriazole with polyethy lene glycol 300; [R-CH2CH2-COo-CH2CH2: where R = 3'-tert-butyl-4'-hydroxy-5'-2H benzatriazol-2-ylphenyl, 2-[2'-hydroxy3'-(o,a-dimethylbenzyl)-5'-( 1,1,3,3-tetramethylbutyl)-

phenyl]benzotriazole; 2-[2'-hydroxy-3'-(l,1,3,3-tetramethylbutyl)-5'-(a,adimethyibenzyi)-

phenyl] benzatriazole.

2.2. 2-Hvdroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4octyloxy, 4-decyl-

oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, as for example 4-tertbutyl-phenyi salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben-

zoyl) resorcinol, benzoyi resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tertbutyl-4-hydroxybenzo-

ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tertbutyl-4-hydroxy-

benzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyi-4hydroxybenzoate.

2.4. Acrylates, for example ethyl c -cyano-,B,,B-diphenylacrylate, isooctyl a-cyano-p, -diphe-

nylacrylate, methyl cr-carbomethoxycinnamate, methyl a-cyano- -methyl-pmethoxy-cinna-

mate, butyl a-cyano- -methyl-p-methoxy-cinnamate, methyl a-carbomethoxy-pmethoxycin-

namate and N-( -carbomethoxy- -cyanovinyl)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis-[4(1,1,3,3-tetrame-

thylbutyl)phenol], such as the 1:1 or 1:2 complex, with or withoutadditional ligands such as n-

butylamine, triethanolamine or N-cyclohexyidiethanolamine, nickel dibutyidithiocarbamate,

- 44 nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-

butyibenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2hydroxy4-methylphe-

nyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5hydroxypyrazole, with or without additional ligands.

2.6. Stericaliv hindered amines, for example bis(2,2,6,6-tetramethyl4piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis( 1, 2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6tetramethyl-4-piperidyi)sebacate, bis(1,2,2,6,6-pentamethyl4-piperidyl) nbutyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2hydroxyethyl)-

2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-

dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyi-4-piperidyl) nitrilotriacetate, tetrakis(2,2,6,6-

tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, 1,1'-(1,2ethanediyl)-bis(3,3,5,5-

tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4stearyloxy-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-1,3,8-triazaspiro[4.5] decan-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetrame-

thylpiperidyl)succinate, linear or cyclic condensates of N,N'-bis-(2,2,6, 6-tetramethyl-4-piperi-

dyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-

aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-nbutylamino-1,2,2,6,6-pen-

tamethylpiperidyl)-1,3,5-triazine and 1,2-bis-(3-aminopropylamino)ethane, 8-acetyl-3-dode-

cyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl1-(2,2,6,6-tetrame-

thyl-4-piperidyl)pyrrolidin-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl4-piperidyl)pyrroli-

dine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6tetramethylpiperidine, a condensation product of N,N'-bis(2,2,6,6tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6dichloro-1,3,5-triazine, a condensation product of 1,2-bis(3-ami-

nopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4butylamino-2,2,6,6-te-

tramethylpiperidine (CAS Reg. No. [136504-96-6]); N-(2,2,6,6-tetramethyl4-piperidyl)-n-do-

decylsuccinimid, N-(1,2,2,6,6-pentamethyi-4-piperidyl)-ndodecylSuccinimid, 2-undecyl-

7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-

tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4,5]decane und epichlorohydrin, 1,1 bis( 1,2,2,6,6-pentamethyi4-piperidyloxycarbonyl)-2(4-methoxyphenyl)ethene, N, N'-bis

- 45 formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, diester of 4-methoxy-

methylene-malonic acid with 1,2,2,6,6-pentamethyl4-hydroxypiperidine, poly[methylpropyl-3-

oxy4-(2,2,6,6-tetramethyl4-piperidyl),siloxane, reaction product of maleic acid anhydride-cc-

olefln-copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6pentamethyl4-

aminopiperidine. 2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2, 2'-diethoxyoxanilide, 2,2'-dioctyloxy-

5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2ethoxy-2'-ethy.oxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxydisubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.

2.8. 2-(2-HYdroxYphenYi)-1 375-triazines, for example 2,4,6-tris(2hydroxy-4-octyloxyphenyl)-

1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)4,6-bis(2,4-dimethylphenyl)1,3,5-triazine, 2-

(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4bis(2-hydroxy-4-pro-

pyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy4octyloxyphenyl)4,6-bis-

(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)4,6bis(2,4-dimethylphe-

nyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecylOxyphenyl)-4,6-bis(2,4dimethylphenyl)-1,3,5-tri-

azine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyi]4,6-bis(2,4dimethyl)-1,3,5-tri-

azine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4dimethyl)-1,3,5-

triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl] -4,6-bis(2,4-di-

methylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-

bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)pheny.-4, 6-diphenyl-1,3,5-

triazine, 2-(2-hydroxy4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6tris[2-hydroxy4-(3-

butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)4-(4methoxyphenyl)-

6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2hydroxypropyloxy]phenyl}-

4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. 3. Metal deactivators, for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N,N'bis(salicyloyl) hydrazine, N,N'-bis(3,5-di-tert-butyl-4hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxaly.' dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'bis(salicyl-

oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

- 46 4. Phosphites and phosPhonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phos^ phite, distearyl pentaerythritoi diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butyiphenyl) pentserythritol diphosphite, bis(2,6-di-

tert-butyl-4-methylphenyl)-penteerythritol diphosphite, diisodecyloxypenteerythritol di-

phosphite, bis(2,4-di-tert-butyl-6-methyiphenyl)penteerythritol diphosphite, bis(2,4,6-tris(tert-

butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-bu-

tylphenyi) 4,4'-biphenylene diphosphonite, 6-isooctyioxy-2,4,8,10-tetratert-butyl-12H-di-

benz[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,1 0-tetra-tert-butyl-1 2methyl-dibenz[d,g]-

1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyi-6-methylphenyl) methyl phosphite, bis(2,4-di-tert-

butyl-6-methylphenyl) ethyl phosphite, 2,2',2"-nitrilo[triethyltris(3,3', 5,5'-tetra-tert-butyl-1,1'-

biphenyi-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1, 1'-biphenyl-2,2'-di-

yi)phosphite. Especially preferred are the following phosphites: Tris(2,4di-tert-butylphenyi) phosphite (Irgafos 168, Ciba-Geigy), tris(nonylphenyl) phosphite, (CH3)3C C(CH3)3 (CH3)3C C(CH3)3

(A) H C 2 C (CHg3 P-O-CH CHi+ N

- 47 (CH3)3C C(CH3)3

(CH3)3C P-O CH2CH(C4Hg)CH2CH3 (C) C(CH3)3

(CH3)3C 'oXo' C(CH3)3 (D) C(CH3)3 (CH3)3C

C(CH3)3 (CH3)3C

H Cat-O-Px X P CH3 (E) C(CH3)3 (CH3)3C

H3C-C-CH3

(F) H37Cis O P oX P-O-C,8H37 '1 O -OCH2CH3 (G C- \ 1

5. Hvdroxylamines, for example, N,N-dibenzylhydroxylamine, N,Ndiethylhydroxylamine, N,N-

dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,Nditetradecylhydroxylamine, N,N-

dihexedecylhydroxylamine, N,N-dioctadecyltydroxylamine, N-hexadecyl-Noctadecylhy-

droxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,Ndialkylhydroxylamine derived from hydrogenated tallow amine.

- 48 6. N'trones, for example, N-benzyl-alpha-phenyl-nitrone, N-ethylaipha-methyl-nitrone, N-oc-

tyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecylalpha-tridcyl-nitrone, N-

hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexedecyl-

alpha-heptadecyi-nitrone, N-ocatadecyl-alpha-pentadecyl-nitrone, Nheptadecyl-alpha-hep-

tadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from N,N-dialkylhy-

droxylamine derived from hydrogenated tallow amine.

7. Th osvnernists, for example, diiauryl thiodipropionate or distearyl thiodipropionate.

8. Peroxide scavengers, for example esters of p-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto-

benzimidazole, zinc dibutyidithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis( -

dodecylmercapto)propionate. 9. Polyamide s ab lisers, for example, copper salts in combination with iodides and/or phos-

phorus compounds and salts of divalent manganese.

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

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

12. Fillers and reinforcinq anents, for example, calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, ksolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.

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

14. Benzofuranones and indolinones, for example those disclosed in U.S. 4, 325,863; U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A4316611;

DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2acetoxyethoxy)-

phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2stearoyloxyethoxy)phe-

nyi]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy] phenyl)benzofuran-2-

one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy3,5-dimethylphe-

nyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyi4pivaloyloxyphenyl)-5,7-di-tert-butyl-

benzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2one, 3-(2,3-di-

methylphenyl)-5,7-di-tert-butyl-benzofuran-2-one. The conventional additives are judiciously employed in amounts of 0.1-10 % by weight, for example 0.2-5 % by weight, based on the material to be stabilized.

Costabilizers optionally to be added to the stabilizer mixture of the invention are preferably further light stabilizers, for instance those of the 2-hydroxyphenyl-benztriazole, 2-hydroxyphenyl-triazine, benzophenone or oxalanilide classes, e.g. as described in EP-A-

453396, EP-A434608, US-A-5298067, WO 94/18278, GB-A-2297091 and WO 96/28431, and/or further hindered amines derived from 2,2,6,6tetrasikylpiperidine containing at least one group of the formula G-CH2 jCH3 ? >A G-CH2 CH3

in which G is hydrogen or methyl, especially hydrogen; examples of tetraalkylpiperidine derivatives which can be used as costabilizers with mixtures of

- 50 the invention are given in EP-A-356 677, pages 3 - 17, sections a) to f). These sections of this EP-A are regarded as part of the present description.

Especially preferred as costabilizers are 2-hydroxyphenyl-benztriazoles and/or 2-

hydroxyphenyl-triazines. Of particular interest is the use of compounds of the formula l' es stabilizers in synthetic organic polymers, especially thermoplastic polymers, and corresponding compositions, in film forming binders for coatings and in reprographic material.

The organic materials to be protected are preferably natural, semisynthetic or, preferably, synthetic organic materials. Particular preference is given to synthetic organic polymers or mixtures of such polymers, especially thermoplastic polymers such as polyolefins, especially polyethylene and polypropylene (PP), and coating compositions. Of special importance are also polycarbonates and blends thereof, for example the polymers listed above under items 19 and 28.

Incorporation into the materials can be effected, for example, by mixing in or applying the compounds of the formula 1' and, if desired, further additives by the methods which are customary in the art. Where polymers are involved, especially synthetic polymers, incorporation can take place prior to or during the shaping operation, or by applying the dissolved or dispersed compound to the polymer, with or without subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as latices. A further possibility for incorporating the compounds of the formula 1' into polymers is to add them before, during or directly after the polymerization of the corresponding monomers or prior to crosslinking. In this context the compound of the formula can be added as it is or else in encapsulated form (for example in waxes, oils or polymers). In the case of addition prior to or during the polymerization, the compounds of the formula 1' can also act as a regulator of the chain length of the polymers (chain terminator).

- 51 The compounds of the formula I or 1' can also be added in the form of a masterbatch containing said compound in a concentration, for example, of from 2.5 to 25 % by weight to the polymers that are to be stabilized.

The compounds of the formula i or 1' can judiciously be incorporated by the following methods: - as emulsion or dispersion (e.g. to latices or emulsion polymers), - as a dry mixture during the mixing in of additional components or polymer mixtures, - by direct introduction into the processing apparatus (e.g. extruders, internal

mixers, etc), - as solution or melt.

Novel polymer compositions can be employed in various forms and/or processed to give various products, for example as (to give) films, fibres, tapes, moulding compositions, profiles, or as binders for coating materials, adhesives or putties.

Other materials to be stabilized according to the invention are recording materials. By such materials are meant, for example, those described in Research Disclosure 1990, 31429

(pages 474-480) for photographic reproduction and other reprographic techniques.

The novel recording materials comprise, for example, those for pressuresensitive copying systems, microcapsule photocopier systems, heatsensitive copier systems, photographic material and inkjet printing.

The novel photographic material can be a black and white or a colour photographic material; colour photographic material is preferred. Further details on the structure of colour photographic material, and the components which can be employed in the novel material, can be found, inter alla, in US-A-5,538,840, column 27, line 25, to column 106, line 16, and in the publications cited therein; these passages of US-A-5,538,840 are hereby incorporated by reference. Application of the novel stabilizers of the formula 1' is essentially as described for UV absorbers or hindered amine stabilizers in this reference.

Further important components, especially couplers, are described in US-5, 578,437.

- 52 Likewise of particular interest is the use of the novel mixtures comprising compounds of the formula (I) as stabilizers for coatings, for example for paints. The invention therefore also relates to those compositions whose component (A) is a film-forming binder for coatings.

The novel coating composition preferably comprises 0.01 - 10 parts by weight of (B), in particular 0.05 - 10 parts by weight of (B), especially 0.1 - 5 parts by weight of (B), per 100 parts by weight of solid binder (A).

Multilayer systems are possible here as well, where the concentration of the novel stabilizer (component (B)) in the outer layer can be relatively high, for example from 1 to 15 parts by weight of (B), in particular 3 10 parts by weight of (B), per 100 parts by weight of solid binder (A). The use of the compounds of the formula I or 1' in coatings is accompanied by the additional advantage that it prevents delamination, i. e. the flaking-off of the coating from the substrate.

This advantage is particularly important in the case of metallic substrates, including multilayer systems on metallic substrates.

The binder (component (A)) can in principle be any binder which is customary in industry, for example those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 368-426, VCH, Weinheim 1991. In general, it is a film-forming binder based on a thermoplastic or thermosetting resin, predominantly on a thermosetting resin. Examples thereof are alkyd, acrylic, polyester, phenolic, melamine, epoxy and polyurethane resins and mixtures thereof.

Component (A) can be a cold-curable or hot-curable binder; the addition of a curing catalyst may be advantageous. Suitable catalysts which accelerate curing of the binder are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A18, p.469, VCH Verlagsgesellschaft, Weinheim 1991.

Preference is given to coating compositions in which component (A) is a binder comprising a functional acrylate resin and a crosslinking agent.

Examples of coating compositions containing specific binders are:

- 53 1. paints based on cold- or hot-crosslinkable alkyd, acrylate, polyester, epoxy or melamine resins or mixtures of such resins, if desired with addition of a curing catalyst; | 2. two-component polyurethane paints based on hydroxyl-containing acrylate, polyester or polyether resins and aiiphatic or aromatic isocyanates, isocyanurates or polyisocyanates; 3. one-component polyurethane paints based on blocked isocyanates, isocyanurates or polyisocyanates which are deblocked during baking, if desired with addition of a melamine resin; 4. one-component polyurethane paints based on a trisalkoxycarbonyltriazine crosslinker and a hydroxyi group containing resin such as acrylate, polyester or polyether resins; 5. one-component polyurethane paints based on aliphatic or aromatic urethaneacrylates or polyurethaneacrylates having free amino groups within the urethane structure and melamine resins or polyether resins, if necessary with curing catalyst; 6. two-component paints based on (poly)ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; 7. two-component paints based on (poly)ketimines and an unsaturated acrylate resin or a polyacetoacetate resin or a methacrylamidoglycolate methyl ester; .. 8. two-component paints based on carboxyl- or amino-containing polyacrylates and polyepoxides; 9. twocomponent paints based on acrylate resins containing anhydride groups and on a polyhydroxy or polyamino component; 10. two-component paints based on acrylate-containing anhydrides and polyepoxides; 11. two-component paints based on (poly)oxazolines and acrylate resins containing anhydride groups, or unsaturated acrylate resins, or aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates; 12. two-component paints based on unsaturated polyacrylates and polymalonates; 13. thermoplastic poiyacrylate paints based on thermoplastic acrylate resins or externally crosslinking acrylate resins in combination with etherified melamine resins; 14. paint systems based on siloxane-modified or fluorine-modified acrylate resins;

- 54 15. paint systems, especially for clearcoats, based on malonateblocked isocyanates with melamine resins (e.g. hexamethoxymethylmelamine) as crosslinker (acid catalyzed); 16. UV-curable systems based on oligomeric urethane acrylates, or oligomeric urethane acrylates in combination with other oligomers or monomers; 1 7. dual cure systems, which are cured first by heat and subsequently by UV or electron irradiation, or vice versa, and whose components contain ethylenic double bonds capable to react on irradiation with UV light in presence of a photoinitiator or with an electron beam. In addition to components (A) and (B), the coating composition according to the invention preferably comprises as component (C) a known light stabilizer of the stericaily hindered amine type, the 2-(2-hydroxyphenyl)-1,3,5-triazine and/or 2hydroxyphenyl-2H-benzotriazole type as explained above, examples are mentioned in the above list in sections 2.1, 2.6 and 2.8. Further examples for light stabilizers of the 2-(2-hydroxyphenyi)-1,3,5-triazine type advantageously to be added can be found e.g. in the publications USA4619956, EP-A-

434608, US-A-5198498, US-A-5322868, US-A-5369140, US-A-5298067, WO94/18278, EP-

A-704437, GB-A-2297091, WO-96/28431. Of special technical interest is the addition of the 2-(2-hydroxyphenyl)-1,3,5-triazines and/or 2hydroxyphenyl-2H-benzotriazoles, especially the 2-(2-hydroxyphenyl)-1,3,5triazines.

Component (C) is preferably used in an amount of 0.05 - 5 parts by weight per 100 parts by weight of the solid binder.

Examples of tetraalkylpiperidine derivatives which can be used advantageously as component (C) in coatings are given in EP-A-356 677, pages 3 - 17, sections a) to f). These sections of this EP-A are regarded as part of the present description. It is particular expedient

to employ the following tetrealkylpiperidine derivatives: bis(2,2,6,6tetramethylpiperid-4-yl) succinate, bis(2,2,6,6-tetramethylpiperid-4-yl) sebacate, bis(1,2,2,6,6-pentamethylpiperid4-yl) sebacate, di(1,2,2,6,6pentamethylpiperid-4-yl) butyl-(3,5-di-tert-butyl-4-hydroxybenzyl) malonate,

- 55 bis(1-octyloxy-2,2,6,6-tetramethylpiperid4-yl) sebacate, tetra(2,2,6, 6-tetramethylpiperid-4-yl) butane-1,2,3,4-tetracarboxyiate, tetra(1,2,2,6, 6-pentamethylpiperid-4-yl) butane-1,2,3,4-tetracarboxylate, 2,2,4,4tetramethyl-7-oxa-3,20-diaza-21 -oxo-dispiro[5. 1.1 1.2]heneicosane, 8acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4dione, 1,1 -bis-(1,2,2,6,6-pentamethylpiperidine-4-yl-oxycarbonyl)-2-(4methoxyphenyl)-

ethene, or a compound of the formulae R R R-NH-(CH2)3- N -(CH2)2- N (CH2)3 N H-R

CH3 CH3

C4Hg am< :,N:' N HCH3

N.; < N CH3

where R= I; N-C4Hg H3C <CH3

CH NH CH3

C\H3 R R lCH3 N-(CH2)3- N -(CH2)2- N - (CH2)3 N'R

R CH3 CH3

C4Hg it</ N BRAN -tCHC3H3 NON CH3

where R = N-C4Hg H. C CH3

3 - CH

CH3 1 3

CH3

*- 56 O O) \ 1

C-CH2-CH2-C-O-CH2-CH2 N O

H3C CH m CH3 ICH3

HN IC-CH2-C-CH3

AN 1 (CH2)6 N-

H3C N C H3 H3C

C H3 CH3 CH CH3

N r NON \N 1 (CH2)6 1 3

H3C 7l: N HI NH: ON (CH2)6 N

oder 1 my\' m H Cat, CH3 H3C:: J<CH3 in which m is 5 - 50.

Apart from components (A), (B) and, if used, (C), the coating composition can also comprise further components, examples being solvents, pigments, dyes, plasticizers, stabilizers,

- 57 thixotropic agents, drying catalysts and/or levelling agents. Examples of possible components are those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 429 71, VCH, Weinheim 1991.

Possible drying catalysts or curing catalysts are, for example, organometallic compounds, amines, amino-containing resins and/or phosphines. Examples of organometallic compounds are metal carboxylates, especially those of the metals Pb, Mn, Co, Zn, Zr or Cu. or metal chelates, especially those of the metals Al, Ti or Zr, or organometallic compounds such as organotin compounds, for example.

Examples of metal carboxylates are the stearates of Pb, Mn or Zn, the octoates of Co, Zn or Cu. the naphthenates of Mn and Co or the corresponding linoleates, resinates or tallates.

Examples of metal chelates are the aluminium, titanium or zirconium chelates of acetylacetone, ethyl acetylacetate, salicylaldehyde, salicylaldoxime, o-hydroxyacetophenone or ethyl trifluoroacetylacetate, and the alkoxides of these metals.

Examples of organotin compounds are dibutyitin oxide, dibutyltin dilaurate or dibutyltin dioctoate. Examples of amines are, in particular, tertiary amines, for example tributylamine, triethanolamine, Nmethyidiethanolamine, N-dimethylethanolamine, N-ethylmorpholine, Nmethylmorpholine or diazabicyclooctane (triethylenediamine) and salts thereof. Further examples are quaternary ammonium salts, for example trimethylbenzylammonium chloride.

Amino-containing resins are simultaneously binder and curing catalyst. Examples thereof are amino-containing acrylate copolymers.

The curing catalyst used can also be a phosphine, for example triphenylphosphine.

The novel coating compositions can also be radiation-curable coating compositions. In this case, the binder essentially comprises monomeric or oligomeric compounds containing ethylenically unsaturated bonds, which after application are cured by actinic radiation, i.e. converted into a crosslinked, high molecular weight form. Where the system is UV-curing, it generally contains a photoinitiator as well. Corresponding systems are described in the

- 58 abovementioned publication Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pages 451-453. In radiation-curable coating compositions, the novel stabilizers can also be employed without the addition of sterically hindered amines.

The coating compositions according to the invention can be applied to any desired substrates, for example to metal, wood, plastic or ceramic materials. They are preferably used as topcoat in the finishing of automobiles. If the topcoat comprises two layers, of which the lower layer is pigmented and the upper layer is not pigmented, the novel coating composition can be used for either the upper or the lower layer or for both isyers, but preferably for the upper layer.

The novel coating compositions can be applied to the substrates by the customary methods, for example by brushing, spraying, pouring, dipping or electrophoresis; see also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Voi. A18, pp. 491-500.

Depending on the binder system, the coatings can be cured at room temperature or by heating. The coatings are preferably cured at 50 - 1 50 C, and in the case of powder coatings or coil coatings even at higher temperatures.

The coatings obtained in accordance with the invention have excellent resistance to the damaging effects of light, oxygen and heat; particular mention should be made of the good light stability and weathering resistance of the coatings thus obtained, for example paints.

The invention therefore also relates to a coating, in particular a paint, which has been stabilized against the damaging effects of light, oxygen and heat by a content of the compound of the formula (I) according to the invention. The paint is preferably a topcoat for automobiles. The invention furthermore relates to a process for stabilizing a coating based on organic polymers against damage by light, oxygen and/or heat, which comprises mixing with the coating composition a mixture comprising a compound of the formula (I), and to the use of mixtures comprising a compound of the formula (I) in coating compositions as stabilizers against damage by light, oxygen and/or heat.

The coating compositions can comprise an organic solvent or solvent mixture in which the binder is soluble. The coating composition can otherwise be an aqueous solution or dispersion. The vehicle can also be a mixture of organic solvent and

- 59 water. The coating composition may be a high-solids paint or can besolvent-free (e.g. a powder coating material). Powder coatings are, for example, those described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., A18, pages 438 444. The powder coating material may also have the form of a powder-slurry (dispersion of the powder preferably in water).

The pigments can be inorganic, organic or metallic pigments. The novel coating compositions preferably contain no pigments and are used as a clearcoat.

Likewise preferred is the use of the coating composition as a topcoat for applications in the automobile industry, especially as a pigmented or unpigmented topcoat of the paint finish. Its use for underlying coats, however, is also possible.

The examples below illustrate the invention further. All parts or percentages, in the examples as in the remainder of the description and in the claims, are by weight,

unless stated otherwise. Room temperature denotes a temperature in the range 20-30 C, unless stated otherwise. Data given for elemental analysis are in % by weight calculated (car) or experimentally measured (exp) for the elements C, H and N. In the examples, the following abbreviations are used: % w/w percent by weight; % w/v percent weight by volume; x % (w/v) stands for x 9 solid dissolved . . in 100 ml liquid; m. p. melting point or range; PC polycarbonate; ABS acrylonitrile-butadiene- stryene terpolymer; POM polyoxymethylene; PP polypropylene; LOPE low density polyethylene; DSC differential scan calorimetry; NOR nuclear magnetic resonance (offs, if not otherwise indicated).

- 60 A: PREPARATION EXAMPLES

Example A1: Precursor compound 3,3,5,5-tetroalkyl-piperazin-2,6-dione of the formula O N. O

/ H \ is obtained according to T. Yoshicka et al., Bull. Chem. Soc. Jap. 45,1855-1860 (1972); m.p. 240 - 242 C.

Example A2: in a 1 I three necked flask equipped with a stirrer, thermometer, condenser drying tube and gas inlet tube are placed 94 9 of 3,3,5,5-tetrealkyl-piperazin-2,6-dione (product of example A1) and 57 9 of potassium tert-butoxide in 400 ml of dimethylacetamide.

The reaction is slightly exothermic, the temperature rising to 55 C; to the stirred solution is added dropwise 77 9 of ethyl-bromoacetate, and stirring is continued for 5 hours. The i reaction mixture is cooled to room temperature, then after addition of 200 ml of CH2CI2 is poured into 200 mi of water. The organic layer is separated and concentrated under reduced pressure. The residue is dissolved in toluene, filtered and evaporated under reduced pressure. The product of the formula H3C LO

HN New 3C H O O C2Hs is obtained as a white residue; m.p. 58-60 C.

Example A3: The product of example A2 is charged in a 11 three necked flask equipped with a stirrer, thermometer, condenser drying tube and gas inlet tube with 18 g of p-formaldehyde

-61 in 120 ml of tert-amylalcohol and to the reaction mixture, heated to 75 C, is added dropwise a solution of 24 g of formic acid in 100 ml of tert-amylalcohol. The reaction mixture is heated to 85 C and kept for 6 hours, then cooled to room temperature. A solution of 21 gr of NaOH in 50 ml of water is added. The organic layer is extracted with CH2CI2, washed with water and evaporated under reduced pressure. The product of the formula H3C O

H3C-N NO

H3C H o 0 C2H5 is collected as a white powder. Melting point: 59 C (by DSC) E>(AMPLE A4:

H3C H3

O N O H3C judo O H C H2 C-O N N-CH3

CH, O O CH2

O NEMO

H3C7 N'tCH3 H3C CH3

The product of example As is charged in a 11 three necked flask equipped with a stirrer, thermometer, condenser drying tube and gas inlet tube with 10 g of pentaerythritol in a solution of 120 ml of xylene. 1 9 of lithium amide is added to the stirred solution at 100 C. The reaction mixture is heated slowly to 135 C and kept at this temperature for 24 hours, then cooled to room temperature and filtered and evaporated under reduced pressure. The

- 62 residue is crystallized from hot n-hexane yielding the above product as a white solid of melting range 240 - 244 C.

Elemental Analysis calculated C - 57.0 %, H = 7.4 %, N = 10.8 % measured C = 57.2 %, H = 7.3 %, N = 10.7 % EXAMPLE A8: HO-N N C2-C-Of CH3 H3C:o O C H. CH3 In a three necked flask equipped with a stirrer, thermometer, condenser drying tube and gas inlet tube are placed 94 gr of 3,3,5,5tetraalkyl-piperazin-2,6-dione and 57 gr of potassium tert-butoxide in 400 ml of dimethylacetamide. The mixture is warmed up to 55 C and 77 gr of ethyl-bromoacetate are added dropwise under stirring and left to react for additional 5 hours and cooled down to 25 C. A 200 ml portion of CH2CI2 and 200 ml portion of water is added to the mixture under stirring and the organic layer is collected, dried over Na2SO4 and charged, together with 400 ml of xylene and 22.8 g of di-ethylen glycol, in a round bottomed flask equipped with a stirrer, thermometer, condenser drying tube and gas inlet tube. The solution is heated up to reflux temperature and 0.2 g of di-buthyl tin oxide are added to the mixture and left to react for 12 hours, then cooled down to 25 C. The solution is then concentrated under vacuum and the resulting solid is charged in a round bottomed flask equipped with a stirrer, thermometer, condenser drying tube and gas inlet tube. 350 ml of tert-amyi alcohol and 28g of para-formaldebyde are also charged in the flask and the resulting mixture is warmed up to 75 C and 38.5 g of formic acid is added dropwise under stirring and left to react for 3 hours keeping the temperature at 75 C, then cooled to 25 C. To the mixture are added under stirring 1400 ml of CH2C12 and 42.7 g of a solution of 50 % NaOH in water and left to react for 1 hour at 40 C, then it is cooled down to 25 C. A 2000 ml portion of water and a 1400 ml of ethyl acetate are added to the mixture, the organic layer is separated, dried over Na2SO4 and concentrated under vacuum. The title product is obtained as a white powder of m.p. 59 C (DSC).

- 63 Example A13: O CH3 H3C-N N-(CH2)6 N N-CH3

3 CH3 0 CH3

In a three necked flask equipped with a stirrer, thermometer, condenser drying tube and gas inlet tube are placed 100 gr of 3,3,5,5-tetraalkylpiperazin-2,6-dione and 66 gr of potassium tert-butoxide in 500 ml of N,Ndimethylacetamide. The mixture is warmed up to 55 C and 68.3 gr of 1,6Dibromohexane are added dropwise under stirring and left to react for additional 5 hours and cooled down to 25 C. A 200 ml portion of CH2CI2 and 200 ml portion of water are added to the mixture under stirring and the organic layer is collected, dried over Na2SO4 and evaporated under reduced pressure. The resulting solid is then charged in a round bottomed flask equipped with a stirrer, thermometer, condenser drying tube and gas inlet tube togheter with 600 ml of tert-amyl alcohol and 52 g of pareformaldehyde. The mixture is warmed up to 75 C and 78 9 of formic acid is added dropwise under stirring and left to react for 3 hours keeping the temperature at 75 C, then cooled to 25 C. To the mixture are added under stirring 2000 mi of CH2CI2 and 74 9 of a solution of 50 % NaOH in water and left to react for 1 hour at 40 C, then cooled down to 25 C. A 3000 ml portion of water and a 2000 ml of ethyl acetate are added to the mixture, the organic layer is separated, dried over Na2SO4 and concentrated under vacuum. The title product is obtained asa white powder of m.p. 94 C (DSC) .

Example A24: In a three necked flask equipped with a stirrer, thermometer, condenser are charged 80 ml of N,N-di-methyl-acetamide, 42 9 of 3,3,5,5tetraalkyl-piperazin-2,6-dione and 29 9 of potassium tert-butoxide. The mixture is heated up to 40 C under stirring, then a solution of 19 9 N,NBis-(2-chloro-ethyl)-formamide in 15 ml of N,N-di-methyl-acetamide is slowly added dropwise, keeping the temperature below 80 C and left to react for 3 hours.

The reaction mixture is cooled down to 20 C, 150 ml of methylene dichloride and 120 ml of water are added under stirring, the organic layer is collected, washed with additional 20 ml of water and concentrated under vacuum. A white solid corresponding to the formula

- 64 H3C>r,,J1; J(-CCH3 CH3 CH3

is collected; m.p. 137-139 C.

Example A25: The product of example A24 is charged in a flask equipped with a thermometer and a condenser, dissolved in 120 ml of 37% aqueous HCI, heated up to refluxing temperature and led to react for 3 hours. The mixture is then concentrated under vacuum, the resulting solid is suspended in 400 mi of methylene dichloride and a 20% solution of NaOH in water is added under stirring until the aqueous layer is neutral. The organic layer is collected, dried over sodium sulfate, and concentrated under vacuum yielding a white solid of the formula H3C> N N:; cHa imp 102 CH3 CH3

104 C.

O N O ., Example A17: H. CgO:: CH3 3 CH3 O N 0

:\NJ: 3

H3C H CH3

- 65 A 20.5 g portion of the product of Example A25 is added dropwise over a 30' period time in a three necked flask equipped with a stirrer, thermometer, condenser, containing 100 ml of CH2CI2 and 9.2 g of cyanuric choride cooled down to 5 C and left to react under stirring for 3 hours. A solution of 2 g of NaOH in 8 ml of water are added to the reaction mixture and left to reach room temperature.

Additional 20.5 g portion of the compound are added to the solution under stirring, it is heated up to reboxing temperature for 2 hours, cooled down to 25 C, 10 g of K2CO3 are added to the reaction mixture, heated up again to refluxing temperature for 3 hours and cooled down to 20 C. To the reaction mixture are then added 200 ml of xylene, 10 g of K2CO3 and 7. 7 g of N,N-cyclohexyl-buthyl amine and it is heated up to 1420C for 16 hours under stirring, cooled down to 20 C, washed with 120 ml of water and the organic layer is collected. Evaporation of the solvent under vacuum yields the title product as a white solid of m.p. 64 - 66 C.

Example A21: R-NH-(CH2)6-N(R)-(CH2)6-NH-R H3 H H3

O N O H c'N N -: N:NH NOON CH3

A 80 g portion of the product of Example A25 is added dropwise over 30 minutes in a three necked flask equipped with a stirrer, thermometer, condenser, containing 360 ml of CH2CI2 and 36 g of cyanuric choride cooled to 5 C and left to react under stirring for 3 hours. A solution of 8.6 g of NaOH in 9 ml of water is added to the reaction mixture and left to reach room temperature.

A 25 g portion of N,N-di-buthyl-amine is added to the solution under stirring, heated up to refluxing temperature for 2 hours. Subsequently, a solution of 8.6 9 of NaOH in 9 ml of water is added to the reaction mixture, left to react for 3 hours, the mixture is cooled down to 20 C and the organic layer is separated and washed with 140 ml of water. The organic layer is collected, the solvent evaporated and the resulting solid charged in a three necked flask equipped with a stirrer, thermometer, condenser, containing 300 ml of xylene and 14.3 g of

- 66 bis-(hexametylene)-tri-amine. The reaction mixture is then heated up to 142 C for 16 hours, cooled down to 20 C and washed with 400 ml of water. The organic layer is then concentrated under vacuum obtaining a white solid of m.p. 68 - 77 C.

Elemental Analysis: cal: C61.3,H8.8,N20.4 exp:C61.0,H8.7,N19.9 Examples A5-A7, A9-A12, A14-A16, A18-A20, A22 and A23 The following compounds are obtained in analogy to the method described in the above examples using the appropriate educts: example formula characterization A5,C, O,OCH m 120 C D 2 6 N,NH; -P- SC)

3\ CH CH m 100 2 6 CH, P C (DSC)

A7 HN>( N C-C-O m.p. 97 C (DSC) H3C o H2 H2 CH3 H3C-, O O;CH3

A9 HN N-(CH2)6 N NH m.p. 99 C (DSC) CH3 O CH3

- 67 H3C: O O4,CH3

A10 m.p. 75 C (DSC) H3C-N NO rN N-CH3 H3C O 0 6H2 H2 0 o cH3 3_ Nit 3 O N O

H3C jet N-C-CH-0 m.p. 180 C (DSC) H3C H 0 H2 H2 CH3

H3Cj o 033 m.p. 156 C (DSC) HN NO IN NH

H3C O 0 - H2 H2 - 0 o cH3

- 68 O N O H3C Jo HN N CH2 o O CH3 H3C C-ON m.p. 286 C (DSC) CH3 0 0 CH 'r O CH3 3

O 'N <O

H3C WNJ:CH3

H3C H CH3

H C ICH3 CH

H3C CH3

O N:O A15 O O CH m.P.127 C (DSC) H N\ N N-C-C-O Nit H. r,rH b O H H. CH CH3 3 H3C N N-C\ C2-N; m.p. 54 - 58 C C-O-C-C-O-C

CH3 H2 H2 o CH3 3

- 69 H C CH3 CH

O N O N:,rN, N A18 H3C N. N CH3 m.p. 190 C (DSC) : AN CH3

H3C-N N

CH3 H3C N CH3

3 CH3 CH3

H3C:O O;CH3

Al9 HN N (CH2),0 N NH m.p. 78 C (DSC) 3 CH3 O CH3

A20 H3C N N (CH2),0 N N CH3

3 CH3 O CH3

L. H-NMR (300 MHz, CDCI3 /ppm: 3.72 (t, 4H); 2.32 (s, 6H); 1.48 (m, 4H); 1.36 (s, 24 H); 1.24 (M, 12 H)

- 70 A22 R-NH-(CH2)6-N(R)-(CH2)6-NH-R with m.p. 66 -72 C H3C I 3 CH

R beingH3C ACHE O N O 14H3 \ O

9 4 N N-CH3

NOUN CH3

Elemental Analysis: Cal: C62.3,H9.0,N19.6; exp:C61.7,H8.9,N19.2 H3C TO O4CH3

A23 (A AWN-(CH2),0 N N O {>

H-NMR (300 MHz, CDCI3)/ppm: 3.69 (t, 4H); 3.58 (m, 2H); 2.4 (m, 4H); 1.73 (m, 4H); 1.45 (m, 26 H); 1.22 (m, 26 H).

B: Application Examples Example B1: Light-stabilizing action in polypropylene plaques.

1 g each of the compounds indicated in Table 1 and 1 9 of tris(2,4-di-tbutylphenyl)phosphite, 0.5 g of pentaerythritol tetrakis [3-(3,5-di-tbutyl-4-hydroxy phenyl)propionate], 1 g of calcium stearate and 1 9 of Filofin Blue 4G are mixed in a turbo mixer with 1000 9 of polypropylene powder (MOPLEN_ SSF) of melt index = 3.7 9/10 minutes (measured at 230 C an 2.16 kg).

The mixtures obtained are extruded at a temperature of 200-230 C to give polymer granules which are then converted into plaques of 2 mm thickness by injection moulding at 200 -

220 C. The plaques obtained are exposed in a model 65 WR Weather-O-Meter (ASTM D2565-85) with a black panel temperature of (63+3) C until surface embrittlement (chalking) starts. Further samples are exposed until a roughness parameter Ra=0 5,um is

-7 reached; evaluation is done using a measurement unit for surface texture (Surtronic_ model 3+; Lc=0.8mm; Ln=4.0mm, LO being the cut-off length, i.e. the lenght of the reference line used for identifying the irregularities characterizing the surface and Ln being the total evaluation length).

A plaque of polypropylene prepared under the same conditions as indicated above but without the addition of the compounds of the invention is exposed for comparison.

In Table 1, the exposure time needed is given in hours. The longer the time the better is the stabilizing effect.

Table 1

Stabilizer R==0.5 1lm after (hours) Chalking time (hours) without stabilizer 500 compound of Example A12 3200 3450 compound of Example A13 4090 4020 compound of Example A16 3580 3450 Example B2: Light-stabilizing action in polypropylene tapes.

1 g of each of the compounds listed in Table 2, 1 9 of tris[2,4-di-tertbutylphenyl]phosphite, 0.5 9 of pentaerythritol tetrakis[3-(3,5-di-tertbutyl-4-hydroxy-phenyl)propionate] and 1 g of calcium stearate are mixed in a turbomixer with 1000 g of polypropylene powder (MOPLEN_ SSF, having a melt index of 3.7 measured at 230 C and 2.16 kg).

The mixtures are extruded at 200 - 220 C to give polymer granules which are subsequently converted to stretched tapes of 50 1lm thickness and 2.5 mm width, using a semi-industrial type of apparatus ( Leonard-Sumirago (VA) - Italy) and waking under the following conditions: Extruder temperature: 200-230 C Head temperature: 240-260 C Stretch ratio: 1: 6

- 72 The tapes thus prepared are mounted on a white card and exposed in a Weather-O-Meter 65 WR (ASTM D 2565-85) with a black panel temperature of (63+3) C.

The residual tenacity is measured, by means of a constant velocity tensometer, on a sample taken after various light exposure times; from this, the exposure time (in hours) required to halve the initial tenacity (To) is measured.

By way of comparison, tapes prepared under the same conditions as indicated above, but without the addition of the stabilizers of the present invention, are exposed. The results are shown in Table 2.

Table 2

Stabilizer _ T_ (hours) without stabilizer 500 compound of Example As 1640 compound of Example A10 1610 compound of Example A13 2110 compound of Example A16 1910 Example B3: Light-stabilizing action in polypropylene fibers.

1 9 of the compound indicated in table 3 below together with 1g of calcium stearate, 2.5 g of TiO2 (KronosT RN 57) and a blend of 0.5g of calcium monoethyl 3,5-di-tert-butyl-4-

hydroxybenzyl phosphonate and 0.5 g of tris(2,4-di-tert-butylphenyl) phosphite are mixed with 1000 9 of polypropylene powder (Mopien_ FLF 20; melt flow index 12.2 g/10 min. measured at 230 C and 2.16kg) in a turbo mixer.

The mixtures are extruded at 190-230 C to give granules; these are subsequently converted into fibres using a a semi-industrial type of apparatus (Leonard-Sumirago_ (VA), Italy) under the following conditions: Extruder temperature: 200-230 C Head temperature: 255 C Stretch ratio: 1:3.5 Count: 11 dtex per filament

- 73 The fibres produced in this way are exposed against a white cardboard in a Weather-O-

Meter_ Type 65WR with a black panel temperature of (63 3) C in accordance with ASTM D 2565-85. After various exposure times, the residual tensile strength of the samples is measured by means of a constant-speed tensometer. The exposure time Tso needed to halve the initial tensile strength is then calculated. The results are shown in Table 3 below.

The amount data are based on the weight of the polypropylene employed.

Table 3: Exposure duration (Ts0/h) for the tensile strength to half Stabilizer Tso/h none 300 A21 1100

A22 1 280

The fibres stabilized according to the invention have excellent tenacity.

Example B4: Stabilization of polyethylene films The additives reported in table 4 below are mixed via masterbatch with LOPE pellets (Riblene_ /FF 29; d=0.921g/cm3; MFI (190 C/2.16kg) = 0.60 9/10 min.) in a turbo mixer.

The mixtures are extruded at 200 C to obtain granules that are converted into films of thickness 150 Am by compression molding (170 C/3 min.).

Some of the films are treated with pesticides by storing them before WOM exposure for 20 . days at 30 C over a concentrated solution of VAPAM_ in water (1:1 relation in parts by volume) without direct contact with the solution.

VAPAM_ (BASLINI SpA, Treviglio/BG, Italy) is an aqueous solution of 382 9 per liter of metam-sodium having the formula CH3-NH-CS-SNa.

Film samples are then mounted in quartz tubes and exposed against a white cardboard in a Weather-O-Meter_ (WOM) Type 65 WR with a black panel temperature of (63+3) C. The degradation process is monitored by measuring the increase of carbonyl in the sample with a Fourier Transform Infrared Spectrophotometer. A high increase of carbonyl indicates high

- 74 degradation. The results are given in the following table 4 (arbitrary units). The amount data are based on the weight of the polyethylene employed.

Table 4: Increase of carbonyl concentration (iCO) after the indicated exposure (WOM) Stabilizer iCO after 875 h WOM iCO after pesticide treatment and 765 h WOM none 0.4 0.8 0.3 % A21 0.037 0.072

0.3 % A22 0.046 0.078

It is evident, that the stabilizer of the invention provides effective stabilization for PE films both with and without pesticide treatment.

Example B5: Stabilization of a gray pigmented polycarbonate/ABS blend.

Commercial PC/ABS-blend (Cycoloy_ MC 8002; 50/50 wVwt blend of PC and ABS pigmented with 1 % by weight of Gray 9779 is stabilized by addition of 1 % by weight of 2-(2'-

hydroxy-3',5'-bis(1,1-dimethylbenzyl)phenyl)-benztriazole (C) and 0.5% by weight of the compound indicated in table 5. A sample containing only the 1 % by weight of the benztriazole stabilizer and an unstabilized sample serve as comparison. Izod bars (2.5"L x 0.5"W x 0.125"W) are prepared by injection molding on a BOY 30 machine, barrel temperature 475-

515 F, die temperature 515 F. Accelerated weathering is performed using an Atlas Ci65A Weather-o-meter (XAW), operated in either "Dry XAW" mode (ASTM G26-90 method C).

After regular intervals, the color change AE according to DIN 6174 is determined. Results are i, i compiled in table 5.

Table 5: Color change (AK) of gray pigmented PC after the indicated irradiance time Irradiance time: 94.8 h 500.5 h 999.7 h 1249.0 h Stabilizer_ HE _ AE AE AE none 1.5 6.9 9.8 11.0 C 0.7 4.2 7.7 9.0

C + All 0.5 3.1 6.2 7.2 C + A14 0.2 2.3 5.4 7.0

C + A4 0.3 2.1 5.0 6.5

- 75 C + A17 0.3 1.7 4.3 5.7

- 76 Example B6: Stabilization of a white pigmented polycarbonate/ABS blend.

Samples are prepared from commercial PC/ABS-blend (Cycoloy_ MC 8002; 50/50 wVwt blend of PC and ABS as described in example B5 except that TiO2 (Tiona_ RCL futile; SCM chemicals) is used as pigment. Weathering and assessment is done as described in example B5; results are compiled in table 6.

Table 6: Color change (AK) of white pigmented PC after the indicated irradiance time Irradiance time: 499.3 h 999.8 h 1249.3 h Stabilizer HE _ AE _ HE none 11.6 21.8 23.7 C 6.0 15.7 17.4

C+A11 2.6 10.2 11.7

C + A14 2.3 9.3 11.3

C+A4 2.7 9.6 11.4

C + A17 2.2 9.2 10.7

PC/ABS samples stabilized according to the invention show an excellent color stability.

Example B7: Gloss and Chip Impact Strength of stabilized PC/ABS Further samples prepared and exposed to weathering as shown in examples B5 and Be are assessed in respect of gloss and chip impact strength.

Gloss: 2"x2" injection molded plaques are removed and replaced at each interval.

Measurement device is BYK-Gardner Haze-Gloss Laboratory Reference Instrument.

Chip impact testing: 10 replicate bars are used for each test interval, impacting the exposed face. Test conducted per ASTM D4508-90 using TMI Monitor/lmpact Tester.

PC/ABS samples stabilized according to the invention with 0.5 % by weight of the compound of example A4 or A17 show excellent gloss retention and impact strength.

Example Be: Stabilization of a 2-coat metallic finish The lightstabilizers to be tested are dissolved in 30 g of Solvesso 100 and tested in a clearcoat having the following composition (parts by weight):

- 77 Synthacryl SC 303 27.51 Synthacryl SC 370 2) 23.34 Maprenal 650 3) 27.29 Butyl acetate/Butanol (37/8) 4.33 Isobutanol 4.87 Solvesso 150 4) 2. 72 Crystal Oil K-30 s, 8.74 Levellinn assistant Bavsilon MA 6) 1.20 1 00. 00

Acrylate resin, Hoechst AG; 65 % solution in xylene/butanol (26:9) 2Acrylate resin, Hoechst AG; 75 % solution in Solvesso 1004 3 Melamine resin, Hoechst AG; 55 % solution in isobutanol 4 aromatic hydrocarbon mixture, boiling range: 182-203 C (Solvesso 150) or 161 - 178 C (Solvesso 100); manufacturer: basso 5aliphatic hydrocarbon mixture, boiling range: 145 - 200 C; manufacturer: Shell 61 % in Solvesso 150; manufacturer: Bayer AG 1 % of the light-stabilizers to be tested is added to the clearcoat, based on the solids content of the varnish. For comparison, a clearcoat containing no light-stabilizers is used.

The clearcoat is diluted with Solvesso 100 to spray viscosity and is applied by spraying to a prepared aluminium panel (@Uniprime Epoxy, silver-metallic basecoat) which is baked at 130 C, for 30 minutes, to give a dry film thickness of 40 - 50 1lm of clearcoat.

me. The samples are then weathered in an Atlas UVCON weathering unit (UVB313 lamps) in a cycle comprising UV irradiation at 70 C for 4 hours and condensation at 50 C for 4 hours.

The surface gloss (20 gloss as defined in DIN 67530) of the samples is then measured at regular intervals. The results are shown in Table 8.

- 78 Table 8:

Light-stabilizer 20 * gloss as defined in DIN 67530 after hours weathering in the UVCON (UV8-313) ..... -

0 hours 400 hours ...._._

None 93 77 A7 93 83

AS 93 85

AS 93 86

. . _ _

A10 93 81

_... A12 93 86

_.. _.... _

A13 93 89

_ _.. _ _

* high values indicate a good stabilization In The results listed in Table 8 show that the samples stabilized with a stabilizer according to the invention have better weathering stability (gloss retention) than the unstabilized sample.

Example B9: Stabilization of Thermoplastic Olefins Molded test specimens are prepared by injection molding thermoplastic olefin (TPO) pellets containing pigments, a phosphite, a phenolic antioxidant or hydroxylamine (HA), a metal stearate, ultraviolet light absorbers (UVA) or a hindered amine stabilizers (HALS) or a mixture of UV absorbers and hindered amine stabilizers as described below.

Pigmented TPO pellets are prepared from pure pigment or pigment concentrates, stabilizers, co-additives and commercially available thermoplastic olefin by mixing the components in a Superior/MPM 1" single screw extruder with a general all-purpose screw (24:1 L/D) at 400 F (200 C), cooled in a water bath and pelletized. The resulting pellets are molded into 60 mil (0.006 inch thick) 2"x2" plaques at about 375 F (1 90 C) on a BOY 30M Injection Molding Machine. Pigmented TPO formulations composed of polypropylene blended with a rubber modifier where the rubber modifier is an in-situ reacted copolymer or blended product containing copolymers of propylene and ethylene with or without a ternary component such as ethylidene norbornene are stabilized with a base stabilization system consisting of an N,N

- 79 dialkylhydroxylamine or a hindered phenolic antioxidant with or without an organophosphorous compound.

All additive and pigment concentrations in the final formulations are expressed as weight percent based on the resin.

Formulations contain thermoplastic olefin pellets and one or more of the following components; 0.0% - 2.0% pigment, 0.0% - 50.0% talc 0.0% - 0.1% phosphite, 0.0% - 1.25% phenolic antioxidant, 0.0% - 0.1% hydroxylamine, 0.05% - 0.10% calcium stearate, 0.0% - 1.25% UV absorber, 0.0% -1.25% hindered amine stabilizer (HALS).

The components are dry blended in a tumble dryer prior to extrusion and molding.

Test plaques are mounted in metal frames and exposed in an Atlas Ci65 Xenon Arc Weather-o-meter at 70 C black panel temperature, 0.55 W/m2 at 340 nanometers and 50% relative humidity with intermittent ilghVdark cycles and water spray (Society of Automotive Engineers - SAE J 1960 Test Procedure). Specimens are tested at approximately 625 kilojoule intervals by performing color measurements on an Applied Color Systems spectrophotometer by reflectance mode according to ASTM D 2244-79. Data collected include delta E, L*, a* and b* values. Gloss measurements are conducted on a BYK-

GARDNER Haze/Gloss Meter at 60 according to ASTM D523.

UV Exposure Testing Test specimens prepared from a commercially available polyolefin blend (Polytrope TPP 518-01; commercial supplier A. Schulman, Inc.; Akron, Ohio, U.S.A.) as 60 mil thick 2" x 2" injection molded plaques are exposed to UV radiation under SAE J 1960 - Exterior Automotive conditions.

- 80 The Control sample contains as stabilizer formulation the compound A as indicated in the following table, 0.2 % by weight of compound B and 0. 1 % of a 1:1 mixture of tris(2,4-di-t butylphenyl)phosphite and 1 part of pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxy phenyi)propionate] in the final resin formulation as commonly used in the industry to impart UV stability.

Samples 1-3 stabilized according to the invention contain 0.05% dialkylhydroxylamine in the final resin formulation as base stabilization and 0.2 % by weight of compound C costabilizer.

Compound A is Bis(2,2,6,6-tetramethylpiperidine-4-yl) sebacate; compound B is Poly [[6-[(1,1,3,3-tetramethyi butyl) amino]-1,3,5-triazine-2,4-dlyl] [[(2,2,6,6 tetramethyl-4-piperidyl) imino] hexamethyiene [(2,2,6,6tetramethyl-4-piperidyi) imino]]; CAS No. 70624-18-9; compound C is of the formula R-NH-(CH2)3-N(R)-(CH2)2-N(R)-(CH2)3-NH-R, with R being _ _ (GAS-No. 106990-43-6). Compounds A, C HAN-<'N:N C H.

NAN B and C are commercial stabilizers (Ciba Specialty Chemicals Inc.).

All of the samples contain talc at 15%, 2-(2-hydroxy-3,5-di-tertamylphenyl)-2H-benzb triazole at 0.2%, 0.1 % calcium stearate and as colorpackage 0.25% Red 3B and Pigment Red 177, C.l. # 65300.

All additive and pigment concentrations in the final formulations are expressed as weight percent on the resin.

Table 9: UV exposure testing of Polytrope TPP plaques Sample HALS delta E Gloss NO Gloss Retention = 3000 Kj/m2 3000 Kj/m2 3000 Kj/m2 Control 0.20% A 4.7 5.4 8.1 % _.._ 1 0.20% A9 1.9 21.8 32.1%

2 0.20% A19 2.2 27.2 40.6%

3 0.20% A13 2.3 15 9 27.3%

Samples exhibit exceptional resistance to photodegradation then stabilized with light stabilizer systems comprising a piperazinedione of present invention.

- 81 In all cases, the light stabilized formulations show much greater resistance to photodegradation than unstabilized specimens which fail quickly under the UV exposure conditions outlined above.

Claims (11)

- 82 WHAT iS CLAIMED IS:

1. A compound of the formula (I') or (II) MA (I)

Z. __ \ X R'15 X-_

N N (11)

R. N N-(R gC)-R 15 R O P

wherein p is from the range 1-10; s is from the range 1 to 8; R., Rz, R3 and R4, independently of each other, are C'-C4alkyl; À Rs is hydrogen; C'C'8alkyl; oxyl; OH; CH2CN; C'-C'8aikoxy; C5-C'2cycloalkoxy; C3 C8alkenyl; C3-C8alkynyl; CrC,2phenylaikyl; CrC'sphenylalkyl, which is substituted on the phenyl ring by 1,

2 or 3 radicals selected from C'-C4alkyl and C'C4aikoxy; Cr C'5phenylalkoxy; CrC'5phenylalkoxy, which is substituted on the phenyl ring by 1, 2 or 3 radicals selected from C'-C4alkyl and C,C4aikoxy; or R5 is C'-C8alkanoyi; C3-Csalkenoyl; C,-C'8aikanoyloxy; glycidyl; or a group -CH2CH(OH)-G, in which G is hydrogen, methyl or phenyl; when s is 1, A is C2-C'8alkyl substituted by OR30, wherein R30 is C'-C8alkyl or C,-C8alkanoyi substituted by a residue benzophenonyl or benzophenonylaxy, wherein one or both phenyl rings of the benzophenone moiety are unsubstituted or substituted by OH, halogen, C, C4alkyl and/or C,-C'8alkoxy;

- 83 when s is 2 A is C3-C,5alkylene substituted by one or more OH and/or interrupted by one or more XN X N

oxygen, N N N N, -NH- and/or -NR,o-; or A is C3 Z z N Z C,5alkylene substituted by OH and interrupted by phenylene, C'-C4alkylphenylene, -COO, CONH-; or A is C4-C,2alkenylene or one of the groups of the formulae (lla) - (lle) -R -COO-R,2-OCO-Rg-; -R -CONH-R,3-NHCO-Rg-; -R -COO-R'4NHCO-Rg-; (lla) (lib) (llc) - (Ra-CO) R's - X:,N 'il'Z N N (lid) - ( RgCO) j-Ris - X - (Rg-CO);-R's - (Ra C ), R'5- N:,,N j'Z N N (lie) and when R5 is not hydrogen, A also embraces CrC'0alkylene; C=C,0alkylene interrupted by phenylene or C,-C4alkylphenylene; when s is 3, A is C3-C, Oalkantriyl; C3-C,2alkantriyl substituted by OH andlor interrupted by oxygen, -NH or -NR'o-; or one of the groups of the formulae (Illa) (Ilid)

- 84 R28 0 (Illa) O O R J:X, R,5 R',5 X2 R /

-(R8-CO) Rls XyN:,X-R,siCo-R)i N:N (Illb) - (Rg-CO);-R1s-X -(Rg-CO)j-R1s (R8-CO), R,5 - N.:,,N:'X- Rots 1C>R28) j N. N

z (IIIC) Romeo (ilid) RJ:X- '5 X2 R9/

when s is 4, A is C4-C Oalkantetryl; C4-C 2alkantetryl substituted by OH and/or interrupted by oxygen, NH- or -PRO-; or one of the groups of the formulae (IVa) - (IVd)

- 85 J840 R J x I X2 Rs/ (IVa) / D r-29 - tR8-CO) i R1 s - X, ,N X-Rl15 -X^r, N -: X - R15 tCO-R8) j N N N N (IVb) - (Rg-CO) j-R1s-X X-R1s-(CO-R9) j-

- ( R9-CO) j-R1s (R8-Co).I R1s-N: 'N 'X-R1s tCo-R N < N

X- R1s tCo-R2a) j- (IVC) - ( R9-CO);-Rls R15 tCo-R28); - (R8-CO) j- R15 N:, N::N- R1s co-R2a) N N z (IVd) whensis5, A is C5-C,Oalkanepentayl; C5C'2alkanepentayl substituted by OH and/or interrupted by oxygen, -NH- orNR,0-; or one of the groups of the formulae (Va) - (Vc)

- 86 RaJ X \'C; R. 0 (Va) to o D R15 (CO-R8) j -(R8-CO), R1S-X - r,,N N:XR'15 -X:{, Neat N - R15\CO-R8)j NAN NAN (Vb) - (Rg-CO);-R1s-X X-R1s-(CORg) j-

- (R9-CO);-R1 j R15 (Co-R8)i-

(R8-CO), R1s-N:,wN:rN-R1siCO R28)j N, N X- R 1s CO-R28) j- (Vc) when s is 6, A is C C10alkanehexsyl; C C12alkanehexsyl substituted by OH and/or interrupted by oxygen, -NH- or -NR'o-; or one of the groups of the formulae (Via) - (Vlf) . R8J X 3 X2iR / R3 X5 R30 (Via) R219

- 87 - ( R9-CO) j-R1s R15 tCo-R29)i -(R8-CO). R15 - N:, N.:rN - R1s CoR2a) j N << N

(R30-CO) j-R15-N-R,5 tCO-R31) j- (Vlb) - (Ra-CO) j- R1s Ri5 tCo-Ra) j \ / -(R8-Co) i R1s- N y''N X-R'1s -X n, Nq'N - R1siCO-R8)j-

N:N N N (VIC)

- (Rg-CO)j-R1s-X X-R1s-(CO-Rg) j-

R15 tCO-R8) j-

- (R8-CO) - R1s - X 'N j'X-R'15 -X; Nq' N - R1s iCO-R8) j N:N N N

- (Rg-CO) j-R1s-X N-R1s-(CO-Rg).- (Vld) R15-(CO-Rg) j-

- (R8-CO) j R15 R. tCo-Re)-

- (R8-CO) j- R1 s - N.:,,N,X R 15 Rl15 X N N R,5 iCO-R8);-

N:N N N N:N (Vle) 1 N N;R,siCO-R8)j z R15 (CO-R8) j

- 88 (R8-CO)j-R,s-X rN:,X R',5 N Rt15 X::NqwX-R1stCO-R8)j-

N:N N ' N N:N (Vlfl -(R8-Co)i-R,5 -X X\ N X-R,51CO-R8)i- X-R15tCo-R8)i-

R,5 tCo-R8) j when s is 7, A is CrC,0alkaneheptayl; CrC 2alkaneheptayl substituted by OH and/or interrupted by oxygen, -NH- or -NR,0-; or one of the groups of the formulae (Vlla) - (Vlid) - (R8-CO) j- R,s R,5 co-R8) j-

-(R8-CO) j- Rls- N. r, N,X-R'1s -X i, Nq N -R1s\C>R8)j-

N:N N N

- (Rg-CO)j-Rls-X N-R1s-(CO-Rg) j- (Vlla) R,5-(co-Rg) j-

- (R8-CO) j- R,5 R15 tCo-R8)i - (R8-CO) j- R1s - N.: N:'XR'15 R'15 X N N R1s CO-R8);-

N N N N N. N (Vllb) zz N N;R,s tCo-R8)i- R1s-(CO-Rg);-

R,5 tCo-R8) j -(R8-CO)j-R,s-X:N: 'X R' N: R'15 XiN X-R,5iCO-R8);-

N.: N N N N N (Vllc) -(R8-Co)j-R15-X X N X-R,s5Co-R8)i- N\R1 Co-R8) R15 (Co-R8) j R,5 (Co-R8)

- 89 -(R8-CO)-R1s-X t,N 'X-R'15 R'15 X N x-R1stco-Ra)i-

-(R8-Co)i R15-X X N N R,5-tCO-RB)j- X-R CO-R)- (Vlid) 1 R15 tCO-R8)j-

R15 (C -R8) j when s is 8, A is CB-C10alkaneoctayi; C8-C12alkaneoctayl substituted by OH and/or interrupted by oxygen, -NH- or-NR10-; or one of the groups of the formulae (Vlila) - (Vlilb) -(Ra-CO), R,s R15tCo-Ra)i-

-(Ra-CO) - R's - N. r,N 'X-R''5 -X:: N q' N - R's iCO-R8),-

N:N N:N

- (Rg-CO)'-R's-/N N-R's-(CO-Rg)- (Vlila) - (Rg-CO) -R s R15-(C -Rg),-

- (R8-CO) j R,5 R,5 (Co-R8) j -(R8-CO) j R1s - N. y N. X-R'1 s N R'1s X N q' N - R,5 tCo-R8)i N. N li N. N (Vlilb) - (R8-C ) j R1 s X z N N; R,5 iCO-R8) j- X-R,5-(Co-Rg) j-

R,s (CO-R8) j-

the index i is zero or 1; R and Rg, and Rz8, Rz9, R30, R3', R32 and R33, independently of each other, are methylene, and when R5 is not hydrogen, additionally embrace ethylene; R10 is C,-CBalkyl, C1-C8alkanoyl, C5-C 2cycloalkyl, Crc15phenylaikyl which is unsubstituted or substituted on the phenyl ring by a radical selected from C1-C4alkyl and C1-C4alkoxy; R 2, R13 and R,4, independently of each other, are CrC10alkylene; C3C12alkylene substituted by OH and/or interrupted by oxygen, phenylene, C1C4alkylphenyiene, -NH- or NR10-; C4-C12alkenyiene;

- So -

R,5 and R',5, independently of each other, are C2-C,0alkylene; C3-C, zalkylene substituted by OH and/or interrupted by oxygen, phenyiene, C,C4alkylphenylene, -NH- or -NR,o-; R,6 is C3-C,Oaikantriyl; C3C'2aikantriyl substituted by OH and/or interrupted by oxygen, -NH or -NR, o-; Rat is C4-C,Oalkantetryi; C4-C,2alkantetryl substituted by OH and/or interrupted by oxygen, NH- or-NR'0-; or, is C5-C,Oaikanepentayl; C5-C, 2alkanepentayl substituted by OH and/or interrupted by oxygen, -NH- or-NR, 0-; R,g is C C,Oalkanehexayl; C C,2aikanehexsyl substituted by OH and/or interrupted by oxygen, -NH- or-NR,0-; X is -O-, -NH- or-N(R,0)-; X', X2, X, X4, X5, X6, independently of each other, are -O- or-NH-; 0 4 Y is -Oor a residue of the formula /N R,5 (CO-R g)-NO-R.; O R2 Z stands for halogen, NH2, NHR,o, N(R,0)2 or C,-C4alkoxy; Zen has one of the meanings given for Z or is -X-R',5-XH and N: NOON Z2 is H or a residue of the formula R3 O R4 O 2. Compound of the formula (1') or (11) according to claim 1 wherein p is from the range 2 to 6; s is from the range 2 to 8; R. , R2, R3 and R4, independently of each other, are methyl or ethyl; R5 is hydrogen; C,-C,8alkyl; oxyl; OH; CH2CN; C,-C,8aikoxy; C5-C,2cycloalkoxy; C3 C8alkenyl; Crc'2phenylalkyl; Crc'5phenylalkoxy; or R5 is C,-C8alkanoyl; C3-Csalkenoyl; C,

- 91 C aalkanoyloxy; glycidyl; or a group -CH2CH(OH)-G, in which G is hydrogen, methyl or phenyl; when s is 2 A is C3-C,2alkylene substituted by OH and/or interrupted by oxygen, -NH- or -NR,o-; C4-C,2alkenylene; or one of the groups of the formulae (lla) - (lie) -R8-COO-R,2-OCO-Rg-; -R8 CONH-R'3-NHCO-Rg-; -R8-COO-R'4-NHCO-Rg-; (lla) (lib) (llc) -(Re-CO) - R,5 - X N Liz Nit N (lid) - (Rg-CO)'-R1s - X - (Rg-CO)'-Rls \ -(Rs-CO)-Rls-N NiZ N. N (lie) . and when R5 is not hydrogen, A also embraces C2C'0alkylene; C2-C'Oalkylene interrupted by phenylene or C,C4alkylphenylene; when s is 3, A is C3-C'Oalkantriyl; or one of the groups of the formulae (Illa) - (Ilid) Rla O 0 0 R/:X'-R./ R' s XJ(R/ (Illa)

- 92 -(R8-CO). Rls-X Hi, N.,X- R,s iCO-R2a) j N:N (Illb) - ( Rg-CO) j-R1sx -(Rg-CO); - R,j -(Ra-CO)-R1s- N y N X- R,siCO-R28)j N N z (Illc) 48 0 (Ilid) X3 RJ:X R 6 X2 Rg/ when s is 4, A is C4-C10alkantetryi; or one of the groups of the forrnuiae (IVa) - (IVd) 45;o Al RX X2 Rg/ (IVa) D 1 19 (Ra C )iR1s- X MEN X - R'15-X N X-R,5iCO-R8)j N N N N (IVb) -(Rg-CO)j R1s - X X - R1s - (C O-Rg)j

- 93 - (R9-CO);-R15

(R8 CO) R15- N.:,N::X- R15 (C - R28)I

N, N (IVC) X- Rls tco-R28) j - (R9-CO);-R15 R15 (CO-R28) j -(R8 CO) R1s N:'N)'N-R15 (CO RZ8)j N ' N

Z (IVd) when s is 5, A is C5-C,Oalkanepentayl; or a group of the formula (Va) R|8 0 o O: X2 R9/

RB X' X \X5 R30 (Va) 0 D 1 19 when s is 6, A is C C,Oalkanehexayl; or one of the groups of the formulae (Vlb) - (Vlf) (R9-CO);-R15 R15 (CO R29) !-

- ( R8-CO).' R15 N,N -<N - R,5 -IC R28) I

N KN I (Vlb) (R30 CO) j-R15-N-R,S CO-R31)I

- 94 - (R8-CO) j- R,5 R'5 (co-R8) j-

- (R8-CO) j- R1s - N y N. 'X-R''5 -X -; N.:, N - R,5 1CO-R8) j-

N N N:N (Vlc) - (Rg-CO)j-R,5-X X-R15-(CO-Rg) j-

R15 Co-R8)i-

- (R8-CO) Rt5-X -:,N:rX-R''5 -X^;, N, N - R,siCO-R8)j-

N:N N N

- (Rg-cO)j-R15-X N\-R,5-(CO-Rg) j- (Vld) R,5-(co-Rg) j-

- (R8-CO) j- R15 R1 s (CO-R8) j-

- (R8-CO) j- R15 - N.: N. X R'1s N R'1s X: N q' N - R,5 iCO-R8) j-

N N N N N:N (Vle) Zl'N N - R,5 iCo-R8)i Z R1s (CO-R8) j-

- (R8-Co) i- R,5 - X 'N 'X R 15 R'1s X: N. X - R,5 CO-Re) j-

N:N N N N;N (Vlfl -(R8-CO)j-R1s-X X N X-R151Co-R8)i X-R1 Co-R8)i-

R1s (CO-R8) j-

when s is 7, A is Crc1oalkaneheptayl; when s is 8,

- 95 A is C8-C'Oalkaneoctayl; or one of the groups of the formulae (Vlila) - (Vlilb); the index i is zero or 1; R8 and Rg, and R28, R29, R30, Rat, R32 and R33, independently of each other, are methylene; Rho is C,C8alkyl, C'-C8alkanoyl, Cs-C,2cycloalkyl, CrC 5phenylalkyl; Rat, R,3 and R,4, independently of each other, are C=C,0alkylene; C3-C,2alkylene substituted by OH and/or interrupted by oxygen, -NH- or-NR,0-; C<C'2alkenylene; R,5 and R',5, independently of each other, are is C2-C 0alkylene; C3-C,2alkylene substituted by OH and/or interrupted by oxygen, phenylene, C,-C4alkylphenylene, -NH- or -NR'o-; R16 is C3-C'Oalkantriyl; R,7 is C4-C,Oalkantetryl; R.8 is Cs-C'Oalkanepentayl; X is -O-, -NH- orN(R'0)-; X,, X2, X3, X4, X5, independently of each other, are -O- or-NH-; and Z stands for halogen, NH2, NHR'o, N(R'0)2 or C'-C4alkoxy.

3. Compound of the forrr ula (I') according to claim 1 wherein s is from the range 2 to 6; Rat, R2, R3 and R4, independently of each other, are methyl or ethyl; Rs is hydrogen; C,-C,8alkyl; oxyl; OH; CH2CN; C,-C, 8alkoxy; Cs-c'2cycloalkoxy; C3 C8alkenyl; Crc 2phenylalkyl; Crc'5phenylalkoxy; or R5 is C'-C8alkanoyl; C3-C5alkenoyl; C' C'8alkanoyloxy; glycidyl; or a group -CH2CH(OH)-G, in which G is hydrogen, methyl or phenyl; when s is 2 A is C3-C'2alkylene substituted by OH and/or interrupted by oxygen, -NH- or -NR'o-; C4-C,2alkenylene; or a group of the formula (lla) -R8-COO-R'=OCO-Rg-; (lla) and when Rs is not hydrogen, A also embraces C2-C'Oalkylene; when s is 3, A is C3- C'Oalkantriyl; or one of the groups of the formulae (Illa), (Illb) or (Ilid); when s is 4, A is C4-C'Oalkantetryl; or one of the groups of the formulae (IVa), (IVb) or (IVd); when s is 5,

- 96 A is C5-C Oalkanepentayl; when s is 6, A is one of the groups of the formulae (Vlb) - (Vif); the index i is zero or 1; Rat and Rg, and Rag, R29, R30, R3,, R32 and R33, independently of each other, are methyiene; R'o is C,-C alkyl, C -C, alkanoyl, C5-C,2cycloalkyi; R,2 is C2-C, Oaikylene; C3-C,2alkylene substituted by OH and/or interrupted by oxygen, -NH or -NR'o-; R,5 and R',5, independently of each other, are is C=C, 0aikylene; R.6 is C3-C,Oalkantriyl; R,7 is C4-C,Oalkantetryl; X is -O-, NH- or-N(R,0)-; X,, X2, X3, X4, independently of each other, are -O- orNH-; and Z stands for NHR,o or NtR'o)2.

4. Compound of the Formula (I') according to claim 1 wherein s is 2, 3, 4 or 6; R', R2, R3 and R4 are methyl; R5 is hydrogen; C'-C alkyl; C,-C, 8alkoxy; cyclohexyloxy; ailyi; benzyl; acetyl; C3-C4alkenoyl; glycidyl; when s is 2 A is C3-C,0alkylene substituted by OH or interrupted by oxygen, -NH- or-NR,0-; or a group of the formula -R -COO-R,2-OCO-R9- (lla) ; and when Rs is not hydrogen, A also embraces C2-C,0alkylene; when s is 3, A is a group of the formula (Illa); when s is 4, A is a group of the formula (IVa) or (IVd); when s is 6, A is a groups of the formula (Vle); the index i is zero; R8 and Rg, and R2, R29, R30, R3,, R32 and R33 are methylene; R'o is C,-C alkyl, forrnyl, acetyl, or cyclohexyl; R.2 is C=C, 0alkylene; or C3-C,Oaikylene interrupted by oxygen; R,

5 and R',5, independently of each other, are is CrC,0alkylene; R'7 is C4-C, Oalkantetryl; X is -NH-; X', X2, X3, X4 are -O-; and

- 97 Z stands for N(R,0)2 5. A composition comprising A) an organic material sensitive to damage by light, oxygen and/or heat, and B) as stabilizer a compound of the formula 1' or 11 according to claim 1.

B. A composition according to claim 5 comprising as organic material a thermoplastic organic polymer or a binder for a coating or a photographic material.

7. A composition according to claim 5 comprising from 0.1 to 10 % by weight, based on the material to be stabilized, of the stabilizer of component B.

8. A composition according to claim 5 comprising a further component selected from solvents, pigments, dyes, plasticizers, antioxidants, stabilizers, thixotropic agents, levelling assistants, further light stabilizers, metal passivators, phosphites and phosphonites.

9. A composition according to claim 8 comprising as further component a light stabilizer from the class of the 2-hydroxyphenyltriazines and/or 2hydroxyphenylbenzotriazoles.

10. A process for stabilizing an organic material against damage by light, oxygen and/or heat, which comprises adding to or applying to said material at least one compound of the formula 1' or 11 according to claim 1.

11. The use of a compound of the fonnula 1' or 11 according to claim 1 for stabilizing an organic material against damage by light, oxygen and/or heat.