AU715511B2

AU715511B2 - Carrier-bound light stabilizers and antioxidants as fillers and stabilizers

Info

Publication number: AU715511B2
Application number: AU54514/96A
Authority: AU
Inventors: Andreas Kramer; Daniel Muller; Peter Nesvadba; Alfred Steinmann; Jurg Zingg
Original assignee: Ciba Spezialitaetenchemie Holding AG; Ciba SC Holding AG
Current assignee: BASF Schweiz AG
Priority date: 1995-05-31
Filing date: 1996-05-24
Publication date: 2000-02-03
Anticipated expiration: 2016-05-24
Also published as: KR960041257A; CA2177654A1; EP0745646A1; ES2160793T3; JPH08333522A; EP0745646B1; AU5451496A; ZA964416B; TW416970B; BR9602573A; ATE203256T1; DE59607295D1

Abstract

Cpds. of formulae (I) -(IV) fixed on a support are claimed. The use of the cpds. as fillers, and stabilisers for organic materials against oxidative, thermal or light-induced breakdown esp. as heat stabilisers for thermoplastic polymers and the organic compsns. contg. the cpds. are also claimed. R1,R2 =1-16C alkyl, 5-12C cycloalkyl, Ph or 7-9C phenylalkyl; R4,R5 = R, 1-20C alkyl, Ph or naphthyl opt. substd. with 1-4C alkyl, NH4 or Mr+/r; R6 = H, 1-18C alkyl, 5-12C cycloalkyl, 7-9C phenylalkyl, NH4 or Mr+/r; R7 = 1-18C alkyl, Ph opt. substd. wit 1-4C alkyl, or -(CH2)q-COOR6; R8 = 1-8C alkyl; R9 = H, 1-8C alkyl, O degrees (sic), OH, NO, -CH2CN, 1-18C alkoxy, 5-12C cycloalkyloxy, 3-6C alkenyl or alkynyl, 1-8C acyl, or 7-9C phenylalkyl opt. substd. on the Ph ring with 1-4C alkyl; R10 = -COX5COOR6, glycidyl or -X6COOR6; R11 = H or 1-18C alkyl; R12 = 1-18C alkyl or 2-14C alkenyl; R13 = H or 1-4C alkyl; M = metal cation with valency r; X1 = direct bond, 1-8C alkylene, 2-8C alkylene broken by O or S, -CH2CH(R8)- or gp. of formula (V); X2 = O or NH; X3 = 1-6C alkylene; X4 = O or NR11; X5 = direct bond, 1-8C alkylene, 2-6C alkenylene, =CH(R12) or gps. of formula (VI)-(VIII); X6 = 1-18C alkylene, 2-18C alkylene, 2-18C alkylene broken by O or S, or phenylene; m = 0-2; n = 1-6; p,q = 1 or 2; r = 1-3; when n = 1, then R3 = H, 1-25C alkyl, 5-12C cycloalkyl, Ph opt. substd. with 1-4C alkyl, or a monovalent residue of a hexose or hexitol, and if X2 = O, then R3 may = NH4 or Mr+/r; or, when n = 2, then R3 = 2-12C alkylene, 4-12C alkylene broken by O or S, or a divalent residue of a hexose or hexitol; or when n = 3, then R3 = -CH2-CH-CH2- or a trivalent residue of a hexose or hexitol; or when n = 4, then R3 = 4-10C alkane tetrayl or a tetravalent residue of a hexose or hexitol; or when n = 5, then R3 = a pentavalent residue of a hexose or a hexitol; or when n = 6, R3 = gp. (IX) or a hexavalent residue of a hexitol. The cpds. adhere well to the support and are not easily extracted by solvents, e.g. alcohols or hydrocarbons.

Description

Our Ref: 594360 P/00/011 Regulation 3:2

AUSTRALIA

Patents Act 1990

ORIGINAL

COMPLETE SPECIFICATION STANDARD PATENT 0g *r a a

I

a 00

O•

Applicant(s): Address for Service: Invention Title: eiba-Geigy -A6 Klybeckstrasse 141 CH- "-Basl 4051 B se

SWITZERLAND

DAVIES COLLISON CAVE Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 Carrier-bound light stabilizers and antioxidants as fillers and stabilizers The following statement is a full description of this invention, including the best method of performing it known to me:- 5020 A-204571A -1- Carrier-bound light stabilizers and antioxidants as fillers and stabilizers The present invention relates to carrier-bound light stabilizers and antioxidants, to compositions comprising an organic material, preferably a polymer, and the carrier-bound light stabilizers and antioxidants, and to the use thereof as fillers and for stabilizing organic materials against oxidative, thermal and/or light-induced degradation.

The addition of fillers to organic materials, especially polymers, is known and is described for example in H.S. Katz/J.V. Milewski Handbook of Fillers for Plastics, Van Nostrand Reinhold Publishers, New York 1987; in R. GAchter/H. MOller Plastics Additives Handbook, 3rd ed., pages 525-591, Hanser Publishers, Munich 1990; und Ullmann's Encyclopedia of Industrial Chemistry, Vol. A20, pages 494-497, 5th edition, VCH Verlagsgesellschaft, Weinheim 1987. The use of fillers in polymers has the advantage that it is possible to bring about improvement in, for example, the mechanical properties, especially the density, hardness, rigidity or impact strength of the polymer. Since the fillers are often less expensive than the pure polymers, the replacement of part of the expensive pure polymers by fillers also leads to a reduction in the cost of the polymer.

0** For the purpose of improving the adhesion and compatibility of the fillers with the organic S: materials, the fillers are preferably provided with a coating before being employed in the organic materials, preferably polymers. As is evident from the literature references men- S tioned at the outset, US-A-1 264 092, US-A-1 832 416, US-A-1 832 417, US-A-2 199 710, US-A-2 345 191, US-A-2 374 741, US-A-2 663 695, EP-A-0 038 620, US-A-4 283 316, US-A-4 420 341, US-A-4 795 767, CS-B-208 547 100, 193080r) or CS-B-225 404 S 102, 150464t), coating of the fillers is carried out, for example, using fatty acids, especially stearic acid or palmitic acid, with hydrocarbons, with waxes or with so-called adhesion promoters as disclosed in Chapter 9.3.5 of R. Gachter/H. MOller Plastics Additives Handbook, 3rd ed., pages 544-546, Hanser Publishers, Munich 1990.

EP-A-0 038 620 discloses the coating of fillers with thermally labile acidic sulfur compounds which decompose when the coated filler is incorporated into the polymer, forming vulcanization-active sulfur compounds.

-2- US-A-4 420 341 discloses the coating of fillers with oxidation-sensitive unsaturated fatty acids stabilized with antioxidants.

CS-B-208 547 100, 193080r) likewise desribes the coating of fillers, especially calcium carbonate, with C 12

-C

22 fatty acids, followed by stabilization of this coat with antioxidants.

CS-B-225 404 102, 150464t) discloses the coating of mica as filler for polypropylene with silanes, especially triethoxyvinylsilane, and subsequent stabilization of this coat with antioxidants, for example distearyl thiodipropionate or tris(alkylphenyl) phosphites.

The known coating compositions or adhesion promoters do not in all respects satisfy the exacting demands which should be met by a coating composition for a filler which is to be employed in an organic material, especially a polymer.

A coating of fillers for organic materials, especially polymers, which consists exclusively of an antioxidant and/or light stabilizer has not been disclosed in the literature, and is therefore a subject of the present application.

"1 o The stabilization of organic materials, especially polymers, with antioxidants from the class of the sterically hindered phenols is known, for example, from US-A-3 839 278, US-A-4 032 562, US-A-4 058 502, US-A-4 093 587 and US-A-4 132 702. Sterically hindered amines, including in particular compounds comprising 2,2,6,6-tetramethylpiperidyl groups, are preferably employed as light stabilizers ("hindered amine light stabilizers"; HALS).

It has now been found that a selected group of such antioxidants from the class of the sterically hindered phenols, thioalkylcarboxylic acids and thioalkylcarboxylic esters, and a se- S: lected group of light stabilizers from the class of sterically hindered amines, are particularly suitable as stabilizers for organic materials and, simultaneously, as coating compositions for fillers which are employed in organic materials sensitive to oxidative, thermal and/or lightinduced degradation.

The present invention therefore relates to an oxide-, hydroxide-, silicate- or carbonate-based filler coated with a compound of the formula I, II, III and/or IV L(R2)m

R

HO l0R 0:0 (R 2 )m (II)P 0@S@ 0* 9 0 00 0 RF SC OPC*R 00

CH

006 6 00 0000 0 0 R sCBlakl ,-lC~oakl h nlo 7Cpeyakl R2isClC~akyC,-C2C~oakyphny o 7-gpeyllkl R4 is hyrgnItColynpthlo hnlwihi nustt do ssbtttdb 0OC~lkl am onu orill) 0r Rs i hyrogn, l-Coalylnaphhylor henl wichis nsubtittedor s sbsttutd b C*Cakl amonu orH 3 @00r

R

6 is hydrogen, Cl-Cl 8 alkyI, 0 5

-C

12 cycloalkyl, 0 7 -Ogphenylalkyl, ammonium or r

R

7 is Ci-C 18 alkyl, phenyl which is unsubstituted or is substituted by Cl-C 4 alkyI; or

(CH

2 0 2

R

6

R

8 is C 1 -CaakyI,

R

9 is hydrogen, C 1

-C

8 alkyI, OH, NO, -CH 2 CN, Ci-O 18 alkoxy, 0 5

-C

12 cycloalkyloxy,

C

3 -C,,alkenyl, C 3

-C

6 alkynyl, CI-C 8 acyI, 0 7 -Cgphenylalkyl which is unsubstituted or is substituted on the phenyl ring by Cl-C 4 alkyl, 0SS0 0 ois 0C-XE--C00R 6 ,-CHj-CH-H 2 or-X6C001 6 Ri 1 is hydrogen or Ci-Ci 8 alkyl,

R

1 2 is CI-Cl 8 alky or C 2 -Cl 4 alkenyI,

R

13 is hydrogen or Ci-C 4 alkyl, M is an r-valent metal cation, is a direct bond, 0 1

-C

8 alkylene, C 2

-C

8 alkylene which is interrupted by oxygen or sulfur; -CHF-- H- I or HO-0 where R, and R 2 are as defined R8- I R

OH

3 above,

X

2 is oxygen or -NH-,

X

3 is 0 1

-C

6 alkylene,

X

4 isoxygen or

X

5 is a direct bond, 0 1

-C

8 alkylene, C 2

-C

8 alkenylene, OH-R 12

R

13 P-R3or P-R 1 3 0 0 0000 @00000

S

@0 S 0 @0 0 000 0 0000 0 0000 00 0 0 0000 0@ 0e 0 0* 00 0 000 0

X

6 is C 1

-C,

8 alkylene, C2-C, 8 alkenylene, C 2

-C

18 alkylene which is interrupted by oxygen or sulfur; or is phenylene, m is 0, 1 or 2, n is an integer in the range from 1 to 6, pisi1 or 2, q isi1 or 2, r is 1, 2 or 3, and if n is 1,

R

3 is hydrogen, CI-C 25 alkyI, C 5

-C

1 2 cycloalkyl, phenyl which is unsubstituted or is substituted by 0 1

-C

4 alkyl; a monovalent radical of a hexose, a monovalent radical of a hexitol; and, if X 2 is oxygen, R3 is additionally ammonium or M or r if n is 2,

R

3 is 0 2 -Cl 2 alkylene, C 4

-C

1 2 alkylene which is interrupted by oxygen or sulfur; a divalent radical of a hexose or a divalent radical of a hexitol, or if n is 3, 0000 0 0000 00 0 00 00

R

3 is a trivalent radical of a hexose or a trivalent radical of a hexitol, or if n is 4,

R

3 is C 4

-CO

1 alkanetetrayl, a tetravalent radical of a hexose or a tetravalent radical of a hexitol, or if n is -6-

R

3 is a pentavalent radical of a hexose or a pentavalent radical of a hexitol, or if n is 6,

-CH

2

CH-

I I

R

3 is -CH,-C-CH,-O-CH2-C- CH- or a hexavalent radical of a hexitol.

I I

-CH

2 CH2 The expression "an oxide-, hydroxide-, silicate- or carbonate-based filler coated with a compound of the formula I, 11, III and/or IV" is abbreviated in the following paragraphs by the expression "carrier-bound compounds of the formula 1, II, II and/or IV'.

Alkyl having up to 25 carbon atoms is a branched or unbranched radical such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1 ,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl or docosyl. One of the preferred meanings of R 1

R

2 and R 6 is for example

C

1

-C

12 alkyl, especially C 1 -Cloalkyl, for example C 1 -Caalkyl. A particularly preferred meaning S of R 1 and R 2 is for example C 1

-C

6 alkyl, especially C 1

-C

4 alkyl, for example tert-butyl. A particularly preferred meaning of R 3 is C 1

-C

1 1alkyl, especially C 1

-C

1 2 akyl, for example Cl-C 8 alkyl.

A specifically preferred meaning of R 3 is Cl-C 6 alkyl, especially C 1

-C

4 alkyl, for example methyl. A particularly preferred meaning of R 7 is for example C 2

-C

18 -alkyl, especially C4-C14alkyl, for example C 8

-C

14 alkyl. A specifically preferred meaning of R 7 is dodecyl. A preferred meaning of R 2 and R 4 is C 1

-C

1 2 alkyl, especially Ci-Co 10 alkyl, for example C,-C 8 alkyl. A specifically preferred meaning of R 2 and R 4 is C 1

-C

4 alkyl, especially ethyl. A particular meaning of

R

8 is C 1

-C

6 alkyl, especially C 1

-C

4 alkyl, for example methyl. A particularly preferred meaning of R 9 is for example C 1

-C

6 alkyl, especially C 1

-C

4 alkyl, for example methyl. A particularly preferred meaning of R 11 and R 12 is for example Cl-C 12 alkyl, especially C 1 -Cealkyl, for example

C

1

-C

4 alkyl. A particularly preferred meaning of R 13 is for example methyl, ethyl, propyl or tertbutyl, especially tert-butyl and methyl.

C

5

-C

1 2 cycloalkyl is for example cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl or cyclododecyl. A preferred meaning of R 1

R

2

R

3 and R 6 is for example C 5

-C

8 cycloalkyl, esp' pecially C 5

-C

7 cycloalkyl, for example cyclohexyl.

-7- 0 5

-C

12 cycloal kyloxy is for exam pie cyclopentyloxy, cyclohexyloxy, cyclohe ptyloxy, cyclooctyloxy, cyclodecyloxy or cyclododecyloxy. A preferred meaning of R 9 is for example cycloalkyloxy, especially C 5

-C

7 cycloalkyloxy, for example cyclohexyloxy.

Alkenyl having 2 to 14 carbon atoms is a branched or unbranched radical such as, for example, vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. A preferred meaning of R 9 is propenyl and 2-butenyl. A particularly preferred meaning of R 12 is for example C 6 -Cl 4 alkenyl, especially C 8 -Cl 4 alkenyl, for example 0 1 0

-C

1 2 alkenyl.

Alkynyl having 3 to 6 carbon atoms is a branched or unbranched radical such as, for **example, propynyl (propargyl, -CHF-C CH 2-butynyl or3-butynyl.

Acyl having 1 to 8 carbon atoms is for example formyl, acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, benzoyl, acryloyl or crotonyl. Preference is given to

C

1

-C

8 alkanoyll, C 3

-C

8 alkenoyl or benzoyl, especially acetyl.

C

7 -Cgphenylalkyl which is unsubstituted or is substituted on the phenyl radical by Cl-C 4 alkyl, and which preferably contains 1 to 3, especially 1 or 2, branched or unbranched alkyl group radicals is for example benzyl, ax-methylbenzyl, oc,cx-dimethylbenzyl, 2-phenylethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2 ,4-dimethylbenzyl, 2,6-dimethylbenzyl or 4-tert-butylbenzyl. Benzyl is preferred.

Alkenylene having 2 to 18 carbon atoms is a branched or unbranched radical, for example vinylene, methylvinylene, octenylethylene or dodecenyl ethylene. A preferred meaning Of X is for example C 2

-C

6 alkenylene, especially 0 2

-C

4 alkenylene, for example vinylene. A preferred meaning Of X 6 is for example C 2 -Cl 2 alkenylene, especially C 2

-C

8 alkenylene, for example C 2

-C

6 alkenylene.

Naphthyl or phenyl substituted by 0 1

-C

4 alkyl, and which preferably contains 1 to 3, especially 1 or 2, alkyl groups, is for example m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4 dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, phenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 1methylnaphthyl, 2-methylnaphthyl, 4-methylnaphthyl, 1,6-dimethylnaphthyl or 4-tert-butylnaphthyl.

Ammonium is NH 4 A mono-, di- or trivalent metal cation is preferably an alkali metal, alkaline earth metal or aluminium cation, for example Na', Mg", Ca" or Al"'.

C

1

-C

12 alkylene is a branched or unbranched radical such as, for example, methylene, ethy- S lene, propylene, tetramethylene, pentamethylen, hexamethylene, heptamethylene, octa- 6*000 methylene, decamethylene or dodecamethylene. A preferred meaning of R 3 is for example

C

2

-C

1 2 alkylene, especially C 2 -Cloalkylene, for example C2-Caalkylene. A preferred meaning b of X 1 is for example C 1

-C

6 alkylene, especially C 1

-C

4 alkylene, for example C 2

-C

4 alkylene. A specifically preferred meaning of X, is ethylene or propylene. A preferred meaning of X 3 is 0S for example C 1

-C

5 alkylene, especially C-C 4 alkylene, for example methylene. A preferred meaning of X 5 is for example C 1

-C

6 alkylene, especially C 1

.C

4 alkylene, for example ethylene.

A preferred meaning of X 6 is C 1

-C

1 2 alkylene, especially C 1

-C

8 alkylene, for example C 1

-C

4 alkylene, especially methylene.

0005 C2-C, 8 alkylene interrupted by oxygen or sulfur can be interrupted one or more times and is for example -CH 2

-O-CH

2

-CH

2

-S-CH

2

-CH

2

-O-CH

2

CH

2

-O-CH

2

-CH

2

CH

2

-O-CH

2

CH

2

-O-CH

2

CH

2

-CH

2

-(O-CH

2

CH

2 2 0-CH 2 :0.0 -CH 2

CH

2

-(O-CH

2

CH

2 2 0-CH 2

CH

2

-CH

2

-(O-CH

2

CH

2 -30-CH 2

-CH

2

CH

2

-O-CH

2

CH

2 boo -CH 2

CH

2

-(O-CH

2

CH

2 3 0-CH 2

CH

2 Or -CH 2

CH

2

-S-CH

2

CH

2 A preferred meaning of R 3 is, for example, C 2 -Co 10 alkylene interrupted by oxygen or sulfur, especially C 4 -Cloalkylene interrupted by oxygen, for example C 4

-C

8 alkylene interrupted by oxygen. A preferred meaning of

X

1 is for example C 2

-C

6 alkylene interrupted by oxygen or sulfur, especially C 2

-C

6 alkylene interrupted by sulfur, for example C 2

-C

4 alkylene interrupted by sulfur. A particularly preferred meaning of XI is -CH 2

-S-CH

2 A preferred meaning of X 6 is for example C 2

-C

1 2 alkylene interrupted by oxygen, especially C 2

-C

6 alkylen interrupted by oxygen, for example

-CH

2

CH

2

-O-CH

2

CH

2 Phenylene is for example 1,4-phenylene, 1,3-phenylene or 1,2-phenylene. 1,2-Phenylene is preferred.

If R 3 for n 1 to 6 is an n-valent radical of a hexose, this radical is derived, for example, from allose, altrose, glucose, mannose, gulose, idose, galactose or talose; in other words to obtain the corresponding compounds of the formula I it is necessary to replace one, two, three, four, five or six OH groups by the ester group E-1

R

1 O SHO II HO II (E-1)

(R

2 )m X C

O

S in which R 1

R

2 m and X, are as defined above. For example, for n 5 R 3 can be a group 0 -0 O 0- If R3 is the n-valent radical of a hexitol, then the corresponding compounds of formula I are obtained by replacing n OH groups in the hexitols by the abovementioned ester group E-1.

As hexavalent radical of a hexitol Rs can for example be 0 00 o-O-CHb--CH-bCH C H- CH-CH-r-O This group is derived from D-sorbitol.

I I I *I I I Alkanetetrayl having 4 to 10 carbon atoms is for example -CHF-CLHF (pentaerythrityl), C-H CH-CH-CH2- -CHT-CHTCH-CH-GH2- -CHi-CH 7 CHt-;HLH-H- CTH-CH-CH~-CH1- T or

-C~CH

7

H-C

7 CH~H-C~--C P-ntaerythrityl is preferred.

:~eInterest attaches to carrier-bound compounds of the formula 1, 11 and/or 1ll.

Preference is given to carrier-bound compounds of the formula 1, 11 and/or Ill, in which R, is 0 1 -Cl 2 alkyl, C 5

-C

8 cycloalkyl, phenyl or C 7 -Cgphenylalkyl,

R

2 is C 1 -Cl 2 alkyl, 0 5

-C

8 cycloalkyl, phenyl or C 7 -Cgphenylalkyl,

R

4 is hydrogen, C 1 -Cl 2 alkyl, phenyl which is unsubstituted or is substituted by 0 1

-C

4 alkyl; r0 0 ammonium or ML r

R,

5 is hydrogen, C 1

-C

12 alkyI, phenyl which is unsubstituted or is substituted by 0 1

-C

4 alkyl; 000 0 ammonium or r r 900 r+ 00

R

7 is 0 2 -Cl 6 alkyl, phenyl which is unsubstituted or is substituted by 0 1

-C

4 alkyl; or is

-(CH

2 )q---CO 2

R

6

R

8 is C 1

-C

4 alkyI, M is an alkali metal, alkaline earth metal or aluminium, X, is a direct bond, Cl-C 6 alkylene, 0 2

-C

6 alkylene which is interrupted by oxygen or sulfur; or 11

-CH:--CH-

I

or HO C-H- where R, and R 2 are as defined -0-CH 3 6 *000 0 *0000S 0 0O 00 0 0 006 0 0 0000 6 0000 00 0 0 00 0 000 4 above,

X

2 is oxygen or -NH-,

X

3 is Cl-C, 5 alkylene, m is 1 or 2, n is an integer from the range from 1 to 4, pisi1 or 2, q isi1 or 2, r is 1, 2 or 3, and if n is 1,

R

3 is hydrogen, CI-C, 8 alkyl, C 5 -C~cycloalkyl, phenyl which is unsubstituted or is substituted by C 1

-C

4 alkyl; and if X 2 is oxygen, R 3 is additionally ammonium or Y or r if n is 2,

R

3 is C 2

-C

10 alkylene, 0 4 -Cloalkylene which is interrupted by oxygen or sulfur, or if n is 3,

R

3 is c 2 or if n is 4, 00 0 0000 0000 .1 00 00 U 0 00 0O 0 000 0 0 0000 0 0000 00 0 0 00 0 00

R

3 is C 4

-C

8 alkanetetrayl.

-12- Particular preference is given to carrier-bound compounds of the formula 1, 11 and/or 1ll, in which R, is 0 1 -CloalkyI, C 5

-C

6 cycloalkyl, phenyl or benzyl,

R

2 is 0 1

-C

10 alkyI, 0 5 -Crcycloalkyl, phenyl or benzyl,

R

4 is hydrogen, Cl-Cloalkyl, phenyl, ammonium or Mr r

R

5 is hydrogen, 0 1 -Cloalkyl, phenyl, ammonium orMr r 0:0 066: Mr+ 66000: R 6 is hydrogen, Cl-CloalkyI, 0 5

-C

6 cycloalkyl, benzyl, ammonium orr

R

7 is 0 4

-C

14 alkyI, phenyl or 2

COAR

R

8 is methyl, M is an alkali metal, alkaline earth metal oraluminium, X, is a direct bond, 0 1

-C

4 alkylene, C 2

-O

6 alkylene which is interrupted by sulfur; or is j or HO C H- where Rand R 2 are as defined *R2

CH

3 above,

X

2 is oxygen,

X

3 is Cl-C 4 alkylene, misl1or2, n is an integer from the range from 1 to 4, p is 2, q is 2, r is 1, 2 or 3, and if n is 1, -13- 000 0 0 000 0 0:0 0 00

R

3 is hydrogen, 0 1

-C,

2 alkyl, C 5

-C

6 cycloalkyl, phenyi, ammonium or or r if n is 2,

R

3 is C 2

-C

8 alkylene, C 4 -Cl 0 alkylene which is interrupted by oxygen, or if n is 3,

R

3 is ICH -H-CH or if n is 4, CHi--

R

3 is -CHA-C-CH--

CHT

Particular preference is likewise given to carrier-bound compounds of the formula 1, 11 and/or 1l1, in which R, is tert-butyl,

R

2 is C 1

-C

4 alkyl and is ortho to the OH group, and M is 1.

Special interest attaches to carrier-bound compounds of the formula IV, in which R 9 is hydrogen, methyl, 0 8 -Cl 2 alkoxy, cyclohexyloxy or benzyl.

Also preferred are cardier-bound compounds of the formula IV, in which M r+

R

6 is hydrogen, C 1 -Cloalkyl, 0 5

-C

6 cycloalkyl, benzyl, ammonium or r -14-

R

9 is hydrogen, Cl-C,,alkyI, OH, NO, 0 4 -Cl 8 alkoxy, C 5

-C

7 CYCloalkoxy, 02-C 6 acyI, C7-C9phenylalkyl which is unsubstituted or is substituted on the phenyi ring by Cl-C 4 alkyl, 0 0 Rio is -C-X-C0R 6 -CHT--CH-CH 2 or -X 6 O0 6

R

11 is hydrogen or 0 1 -Cl 2 alkyI,

R

1 2 is Cl-Cl 2 alkyI or C 6

-C

14 alkenyI,

R

1 3 is hydrogen or methyl, M is an alkali metal or an alkaline earth metal, 4 is oxygen or

X

5 is a direct bond, Cl-C 6 alkylene, C 2

-C

6 alkenylene, CH R2R1 R13 1 or R1/ X6iCIC2akleeC-C~lknlee 2-lalyen hchi itrrpe b xye;/ri *hnle and orr 0 0 R12 is 0 1

-C

2 alkylee oC-Calkenyln, 0 1 akln hc sitrutdb xgn ri p1heydrnen nd etyl M. risla lal ea orlaln2athmtl )R4 is hyrgeno C-Ray,- ccoexlo

X

5 is a direct bond, Cl-C 6 alkylene, CH-R 12 R13R3o -P ~R 13

X

6 is CI-C 8 alkylene, C 2

-C

8 alkenylene, C 2

-C

8 alkylene which is interrupted by oxygen; or is phenylene, and r is 1 or 2.

:Particular interest attaches to carrier-bound compounds of the formula 1, 11, 111 and/or IV, in 0 a* R, is 0 1 -Cralkyl, cyclohexyl or phenyl, 0:0 R 2 is C,-C 6 alkyI, cyclohexyl or phenyl and is ortho to the OH group, :00:.

so R 3 is hydrogen, Cl-C 8 alkyl, cyclohexyl or

R

4 is hydrogen, CI-C 8 alkyl or Mr+ .00. r *00 0 Rq is hydrogen, 0 1

-C

8 alkyl or r 000 S

R

6 is hydrogen, 0 1

-C

8 alkyI, cyclohexyl or Mr+ 0 r 0 0000 .000 R 7 is C 8 B-Cl 4 alkyl or -(CH 2 q-C0 2 11 6

R

8 is methyl

R

9 is hydrogen, C.,-C 4 alkyl, C 4

-C

12 alkoxy, C 5

-C

7 cycloalkoxy, acetyl or C 7 -Cgphenylalkyl, 0 0 RIO is -C-X-OOR, -CH 2-CH-CH 2 or -X -COR 6 Ril is hydrogen or Cl-C 4 alkyI,

R

12 is C 8 -Cl 4 alkenyl,

R

13 is hydrogen or methyl, -16- M is an alkali metal or alkaline earth metal, OH-CH

X

1 is 0 2

-C

4 alkylene, C 2

-C

4 alkylene which is interrupted by sulfur; or isI R8

X

2 is oxygen,

X

3 is C 1

-C

4 alkylene,

X

4 is oxygen or

X

5 is a direct bond, 0 1

-C

4 alkylene, 7 CH-R3 12 -P R1 3 or *R13, X6i lCakln rpeyee mOs o 2 n s1 Xr is 1 -aln or phn.ee n, is 1, t-utl R3is2,doe r lCakl R4is2 adgn 1CakIoMr hogeal o r R7 is tert-butayl,

R

4 is hydrogen, methalyl BC~loy ylhxlx or ezl -17- 0 0 Rio is -C-X-C0R 6 -CH 2-CH-CH 2 or -X 6COO 6

R

11 is hydrogen,

R

12 is 0 10 -Cl 2 alkenyI, M is calcium, X, is ethylene or ethylene which is interrupted by sulfur,

X

2 is oxygen, X3 is methylene, 4 is oxygen or -NR 11

*OOS

0 000000 00 0O 9 0 000 0 *000

S

0000

OS

00 *6 0 000 S 0* 0 0 0000 *000 00 00 0 00 0 0 000 0 0 0000 0 ObOS 0 0 00 00

X

5 is ethylene or CH -R

X

6 is methylene, m is 1, n is 1, p is 2, and r is 2.

Very particular preference is given to carrier-bound compounds of the formula Ia, lb, Ic, Ila, Ilb, lila and IVa to lWn.

HGC

HOI/ CHi-CHF--COOH 1- 3 C CH 3 1-3C HO CHi-OHl--COOH 1- 3

C

-18- 0@e* 0 @000 0 000000 0 00

S

me. a 0 0O** 0 0@ 0 S S 000 S @0 0O S 5e£* 0*

S

*0 5 4

S

0 0

OS..

60 0 06 0)

HO

CH 3 (Ic) HO CHT-S-CHi--COOH 1- 3 C

OH

3 Hlb HO CH -O HO 3 HOb O ll-P 0- OH 3 H--N NO-CC-l-CHl-OOH 3

CH

OH 3 H 3lCc0 HO CHi--P-OH HO Oc/H 3 0 1 -1Hy-S-Hl-I--Ii-COOH (Il a) (Ilila)

OH

3

H

3 C-N O-C-Hl-O-lOOH

OH

3 (IVb)

OH

3

H

3 0-N N-O-Hl-O---OOH

H

3 0C

OH

3 (lVd) -19-

OH

3

H

3 0 H--N 0-CH -O0H

H

3 0 CH 3 (IVe) OH 3 HG3 H-N NH-OHi--C00H H 3

C

CH 3 (I Vf) 0 @006 0

OS..

0 00060.

S 0 0@

S

6 550 S

S

5050 0 egos 55 00 0 S 5 050 S

OH

3

H

3 0 0 H--N 0-OHi-OH-H 2

H

3 0C

OH

3 (IVg) OH 3

H

3 0C 0 H 3 C 0-OH-O H-H 2 H 3 0C OH 3 (lVh) 5* S S 5055 5555 S S *0 S 55 @0 5 5

OH

3 HOC 0 H3

OH

3

OH

3

H

3 0 0 0 H 10 -N 0-OH -OH-H 2

H

3 0

OH

3 (lvi) (lVk) 5000

S

OS..

55 0 S S 55

OH

3

H

3 0 0 Benzyl-0-,N 0-OH-OH-H 2

OH

3 (lVM)

CH,

H-N

NH-C-CH,-CH-CH=CH-CH-(CH

2 )8-CH 3 HC COOH

CH

3 (IVn) Particular preference is given to carrier-bound compounds of the formula I, II, III and/or IV in which the carrier is a filler or a pigment.

0 The pigments can be inorganic or organic pigments. Examples of particularly preferred inorganic pigments are iron oxides, titanium oxides and zinc oxides. Examples of particularly preferred organic pigments are urea/formaldehyde adducts and aminoanthraquinones.

The preferred fillers are described in H.S. Katz/J.V. Milewski Handbook of Fillers for Plastics, Van Nostrand Reinhold Publishers, New York 1987; in R. Gachter/H. M(ller (eds.), Plastics Additives Handbook, 3rd ed., pages 525-591, Hanser Publishers, Munich 1990; and Ullmann's Encyclopedia of Industrial Chemistry, Vol. A20, pages 494-497, 5th edition, VCH Verlagsgesellschaft, Weinheim 1987.

Special preference is given to acidic-reactive fillers which are able to enter, with the compounds of the formula I, II, III and/or IV, into an acid-base reaction or an adsorption reaction.

0@ Preference is also given to fillers which are able to react with epoxides and to form chemical bonds.

The novel carrier-bound compounds of the formula I, II, III and/or IV are also advantageous in that the compounds of the formula I, II, III and/or IV adhere well to the carrier and cannot very easily be extracted with, for example, an alcohol or hydrocarbon solvent.

Particularly preferred compounds of the formula I, II, III and/or IV are those whose molecule carries at least one free carboxylic acid, one free phosphonic acid or a terminal epoxide.

-21 Preferred fillers are those based on oxide or hydroxide, silicate or carbonate.

Oxide- or hydroxide-based fillers are for example aluminium oxide, magnesium oxide, titanium oxide, silicon oxide, zinc oxide, aluminium hydroxide, magnesium hydroxide or zinc hydroxide.

Silicate-based fillers are for example quartz flour, kieselguhr, talc, aluminium silicate, magnesium silicate, calcium silicate or zeolite.

ego**: 0 Carbonate-based fillers are for example calcium carbonate, magnesium carbonate or dolomite and their various mineralogical forms, for example calcite, chalk or aragonite.

SeeS Very particular preference is given to carrier-bound compounds of the formula I, 11, III and/or IV in which the carrier is an oxide-, hydroxide-, silicate- or carbonate-based filler.

Of specific interest also are carrier-bound compounds of the formula I, 11, 111 and/or IV in l*eee I which the carrier is aluminium oxide, magnesium oxide, titanium oxide, silicon oxide, talc, 5555 calcium carbonate or dolomite.

Special preference is given to carrier-bound compounds of the formula la, Ib, Ic, Ila, lb, Ilia and IVa to IVn in which the carrier is calcium carbonate, titanium oxide or silicon oxide.

Vi l The general term "carrier-bound compounds of the formula I, 11, III and/or IV" is also to be understood, for example, as including "compounds of the formula I, 11, III and/or IV absorbed or adsorbed on a carrier or a support material".

The binding or fixing of organic compounds to carriers, or the coating of fillers with organic compounds, is known and is described, for example, in US-A-4 283 316 (column 3).

The novel carrier-bound compounds of the formula I, 11, III and/or IV can, for example, be prepared as follows: when not already liquid, the compounds of the formula I, 11, III and/or IV are dissolved in an organic solvent, for example ketones, esters, alcohols or hydrocarbons, particular examples being acetone, ethyl acetate or ethanol. The carrier is then added with stirring to the clear solution. The solvent is then removed by distillation, preferably under a -22slight vacuum and in a temperature range from 20 to 2000C. The dry residue provides the carrier-bound compounds of the formula I, 11, 111 and/or IV according to the invention in quantitative yield.

The solvent employed is used in an excess which is expediently from 2 to 20 times, preferably from 4 to 15 times and, in particular, 10 times the amount by weight of the compound of formula I, 11, III and/or IV employed.

0:60 *906 o o Where the compounds of the formula I, II, III and/or IV are acids, for example carboxylic 9 acids or phosphonic acids, these compounds can also be dissolved in an aqueous basic S° solvent, for example dilute alkali metal hydroxide, alkaline earth metal hydroxide or ammo- S nia solution, especially sodium hydroxide solution. This solution is preferably added at S0 slightly elevated temperature to an aqueous suspension of the filler. A preferred reaction temperature is between 30 and 1000C, in particular between 30 and 800C, for example between 40 and 700C. The carrier-bound compounds of the formula I, 11, III and/or IV are preferably isolated by filtering the reaction mixture and then drying the residue under vacuum.

.9 The novel carrier-bound compounds of the formula I, 11, III and/or IV are expediently pre- 0 pared without solvent. In this case the compounds of the formula I, 11, III and/or IV are subjected to intensive stirring with the carrier in a mixer until the mixture has reached a temperature which is about 200C above the melting point of the carrier. Using, for example, calo. cium carbonate as carrier, temperatures of about 150'C are reached in this case. The coarser the carrier, the more rapidly the coating temperature is reached by means of the So frictional heat. Thus, for example, the temperature of calcium carbonate (Millicarb 0 rises to about 1000C in 8 minutes at a stirring speed of about 4000 revolutions per minute. If the desired temperature is not reached in this way with a different carrier, the carrier is preheated in a drying oven, for example, prior to mixing it with the compounds of the formula I, II, III and/or IV.

The novel carrier-bound compounds of the formula I, 11, III and/or IV comprise the compounds of the formula I, 11, III and/or IV in a quantity of for example from 0.01 to 10% by weight, preferably from 0.01 to 5% by weight, for example from 0.10 to 2% by weight, relative to the weight of the carrier.

-23- The compounds of the formula I, II, III and IV can be fixed or bounded to the carrier either individually or as a mixture of different compounds of the formula I, II, III and/or IV. The carriers to be coated, especially fillers, can likewise be employed in pure form or as mixtures of different carriers.

The compounds of the formula I, II and/or III are known and some of them are commercially available, or can be prepared by analogy with the method described in T.H. Coffield et al., J. Amer. Chem. Soc. 79, 5019 (1957); US-A-3270 091; G. Scott et al., Polymer Degradation and Stability 4, 279 (1982) and EP-A-413 562.

Some of the compounds of the formula IV are known and are some are commercially avai- S lable or can be prepared by analogy with the method described in EP-A-0 634 449.

The novel carrier-bound compounds of the formula I, II, III and/or IV are suitable as fillers and for stabilizing organic materials against oxidative, thermal and/or light-induced degradation.

Examples of such materials are: 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1 -ene, poly-4-methylpent- -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 (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods: -24a) radical polymerisation (normally under high pressure and at elevated temperature).

b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either i- or a-coordinated.

These metal complexes may be in the free form or fixed on substrates, typically on 0:0 activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, Ila and/or Ilia of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

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

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; 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 (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

4. Hydrocarbon resins (for example C 5

-C

9 including hydrogenated modifications thereof tackifiers) and mixtures of polyalkylenes and starch.

Polystyrene, poly(p-methylstyrene), poly(ao-methylstyrene).

*ge 6. Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl S acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another S polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrenelethylene/butylene/styrene or styrene/ethylene/propylene/ styrene.

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

8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluo- -26ride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from a,j3-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.

10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or S* acrylonitrile/ alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals 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, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

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

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

Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes 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 -27polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer 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).

C

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, polybutyene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

Polysulfones, polyether sulfones and polyether ketones.

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

22. Drying and non-drying alkyd resins.

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

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

-28- 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.

C

27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homoloo. gous 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, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

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

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

31. Petroleum and coal distillation residues, for example asphalt, bitumen or bituminous materials for road coverings.

-29- The invention therefore also provides compositions comprising an organic material which is subject to oxidative, thermal or light-induced degradation and at least one carrier-bound compound of the formula I, II, III and/or IV.

The organic materials to be protected are preferably natural, semisynthetic or, preferably, synthetic polymers. Particularly preferred polymers are thermoplastic polymers, especially S PVC or polyolefins, in particular polyethylene and polypropylene.

The organic materials to be protected are also preferably asphalt, bitumen or bituminous materials for road coverings, and natural or synthetic polymers suitable for papermaking.

Particular emphasis should be placed on the action of the novel carrier-bound compounds of the formula I, II, III and/or IV against thermal and oxidative degradation, especially under thermal loads as occur in the processing of thermoplastics. The novel carrier-bound compounds of the formula I, II, III and/or IV are therefore outstandingly suitable for use as processing stabilizers.

The carrier-bound compounds of the formula I, II, III and/or IV are preferably added to the material to be stabilized in quantities of from 1 to 50%, for example from 5 to 40%, preferably from 5 to 30%, in particular from 5 to 25%, based on the weight of the organic material.

0 In addition to the novel carrier-bound compounds of the formula I, II, III and/or IV, the novel compositions can comprise further co-stabilizers (additives), for example the following: 1. Antioxidants 1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tertbutyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(oa-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4methoxymethylphenol, 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- 30 m ethyl (1 methyl heptadec- 1'-yl) ph enol1, 2,4-di methyl-6-(1 '-methylt rideo-1 I'-yl) phenol and mixtures thereof.

1 Alkylthiomethylphenols, for example 2,4-d ioctylthiom ethyl-6-te rt-butyl phenol, 2,4-dioctylthiom ethyl methyl phenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonyl phenol.

*00: 1.3. Hydroquinones and alkylated hydroguinones, for example 2,6-di-tert-butyl-4-methoxy- *666: phenol, 2,5-di-tert-butylhydroqui none, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxypheny stearate, bis-(3,5-di-tert-butyl-4hydroxyphenyl) adipate.

1.4. Tocopherols, for example cx-tocopherol, 0-tocopherol, y-tocopherol, 8-tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-butyl-4-methyl phenol), se* 2,2'-thiobis (4-octyl phenol), 4,4'-thi obis(6-tert-butyl-3-methyl phenol), 4,4'-thiobis(6-tert-butyl- 2-m ethyl phenol), 4,4'-thiobis-(3,6-d i-sec-amyl phenol), 4,4'-bis-(2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidenebisphenols, for example 2,2'-methylenebis(6-te rt-butyl methylphenol), 2,2'm ethylenebis (6-te rt-butyl-4-ethyl phenol), 2 ethylenebis methyl (o-methylcyclohexyl)phenol], 2,2'-m ethyl enebis(4-m ethyl-6-cycloh exyl phenol), 2,2'-methylenebis(6-nonyl- 4-methyiphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tertbutyiphenol), ethyl idenebis(6-tert-b utyl-4- iso bu tyl phenol), 2,2'-methylenebis[6-(cm ethyl ben zyl) -4-nonyl phenol], 2 ,2'-methylenebis[6-(c~oc-dimethylbenzyl)-4-nonylphenol], 4,4'-m ethylene bis 6- di-tert-bu tyl phenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1 -bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-m ethyl -2hyd roxybenzyl) -4-m ethyl phenol, 1,1 ,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1 -bis(5-tert-butyl-4-hyd roxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bi s[3 bi s (-te rt- bu tyl -4'-hyd roxyp henyl) buty rate], bis(3-tert-bu tyl hyd roxy-5-m ethylphenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4- 31 methylphenyllterephthalate, 1, 1 -bis-(3,5-di methyl-2-hyd roxyphenyl) butane, 2,2-bis-(3,5-ditert-butyl-4-hydroxyphenyl) propane, 2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-ndodecylmercaptobutane, 1,1 ,5,5-tetra-(5-tert-butyl-4-hydroxy2-methylphenyl)pentane.

1 N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4- hyd roxy-3,5-d i methyl benzylm ercaptoacetate, tri decyl-4- hyd roxy- 0:0 3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4tert-butyl-3- hyd roxy-2,6-d imethyl ben zyl)dithi oterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)su Ifide, isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1 Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1 ,1,3,3tetramnethyl butyl) phenyl]-2,2-bis(3,5-di-te rt-butyl-4-hyd roxybenzyl) malonate.

1.9. Aromatic hydroxybenzyl compounds, for example 1 ,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4, 6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1. .10. Triazine Compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4- 0 hydroxyanilino)- 1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)- 0000 1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)- 1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hyd roxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris-(3,5-di-tert-butyl-4hydroxybenzyl)isocyanu rate, 1, 3,5-tris (4-te rt- bu tyl -3-hyd roxy-2,6- d imethyl ben zyl) isocyanu rate, 2,4,6-tris(3,5 -di-te rt-butyl -4-hyd roxyphenyl ethyl) 3,5-triazi ne, 1 ,3,5-tris(3,5-ditert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1 ,3,5-triazine, 1 ,3,5-tris(3,5-dicyclohexyl-4hydroxybenzyl)isocyanu rate.

1.11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4hydroxybenzyl phosphonate, dioctadecyl-5-te rt-butyl-4-hydroxy-3-m ethyl benzyl phosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

32 1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1. 13. Esters of j3-(3.5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1,9nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bissee: (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl- 1 -phospha-2 ,6,7-trioxabicyclo[2 .2 .2joctane.

1. .14. Esters of f-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexaned iol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanu rate, N, N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri methylol propane, 4-hyd roxymethyl-1 -phospha-2,6, 7-trioxabicyclo[2.2.2]octane.

1.15. Esters of D-(3.5-digyclohexyl-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 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanu rate, N, N'-bis(hydroxysee ethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trim ethylhexanediol, trimethylolpropane, 4-hyd roxym ethyl- 1 -phospha-2 ,6,7-trioxabicyclo[2 .2.2]octane.

1.16. Esters of 3.5-di-tert-butyl-4-hydroxyphenyI acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanu rate, N, N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trim ethyl hexanedi ol, trim ethylolp rpane, 4hydroxymethyl-1 -phospha-2 ,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of 1-(3.5-di-tert-butyl-4-hydroxyohenyl)propionic acid e.g. N, butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N, N'-bis(3,5-di-tert-butyl-4-hydroxy- 33 phenyl prop ionyl)trimethylenediam ine, N, N'-bis(3,5-di-tert-butyl-4-hydroxyphenylp ropionyl)hydrazine.

1.18. Ascorbic acid (vitamin C) 1. 19. Aminic antioxidlants, for example N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-seca:*butyl-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p-phenylenediamine, N, N'-bis(1 *so: ethyl methyl pentyl)-p-phenyl enedi am ine, N, N'-bis(1 -methylheptyl)-p-phenylenediamine, 0000 N, N-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyI-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl)- N'-phenyl-p-phenylenediamine, N-(1 -methylheptyI)-N'-phenyl-p-phenylenediamine, Ncyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N, N -di- :ethyl N'-di-sec-butyl-p-ph enyl ened iam ine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1 -naphthylamine, N-(4-tert-octylphenyl)-1 -naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenyl- .a mine, 4-n-butylam ino phenol, 4-butyrylaminophenol, 4-nonan oyl am ino- phenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-d imethyl am inomethyl phenol, 2,4'-d iam inod iphenyl methane, 4,4'-diaminodiphenyl- S.a methane, N, N, N '-tet ramethyl-4,4'-diam in odi phenyl methane, 1 ,2-bis[(2-methylphenyl)aminojethane, 1, 2-bis(phenylam ino) propane, (o-tolyl)biguanide, Bis[4- ,3'-di methyl butyl) phenyllamine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated a..

0 tert-butyl/tert-octyldiphenylami nes, a mixture of mono- and dialkylated nonyldiphenylamines, ixur f on-and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono- und dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1 ,4-benzothiazine, phenothiazine, a mixture of mono- und dialkylated tert-butyl/tert-octyiphenothiazines, a mixture of mono- und dialkylated tert-octyl-phenothiazines, N-allylphenothiazin, N, N, N'-tetraphenyl-1 ,4-diaminobut-2-ene, N, N-bis(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetram ethyl pi perid-4-yl)sebacate, 2,2, 6,6-tetramethylpiperidin-4-one, 2,2, 6,6-tetramethylpiperidin-4-o.

2. UV absorbers and light stabilisers 2.1. 2-(2'-Hydroxyohenyflbenzotriazoles, for example 2 hyd roxy-5'-m ethyl phenyl) benzotriazole, 2- 5'-di-te rt-butyl hyd roxyphenyl) ben zotri azol e, 2-(5'-tert-butyl-2'-hydroxyphe- 34 nyl)benzotriazole, 2- hyd roxy-5'- 1, 3,3-tetram ethyl bu tyl) phenyl) benzotri azole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphe- 2- (3'-sec- bu tyl -5'-te l- b utyl -2'-hyd roxyph enyl) ben zotri azol e, 2- (2'-hydroxy-4'-octyioxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis-(cz,(x-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, mixture of 2-(3'-tertbutyl-2'-hyd roxy-5'-(2-octyloxycarbonyl ethyl) phenyl)-5-ch lo ro- benzotriazol e, 2-(3'-tert-butyl- *:06 5'-[2-(2-ethyl hexyl oxy) -ca rbo nyl ethyl] -2'-hyd roxyphenyl) -5-chlIoro- benzot riazole, 2-(3'-tert- 000: butyl -2'-hyd roxy-5'-(2-m ethoxycarbonyl ethyl) phenyl) -5-chloro-benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl) benzotriazole, 2-(3'-tert-butyl-2'-hyd roxy-5'-(2octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hyd roxyp he nyl) ben zotriazole, 2- (3'-dodecyl -2'-hyd roxy-5'- methyl phe nyl) be nzot ri azole, and 2-(3'-te rt- butyl -2'-hyd roxy-5'-(2-isooctyl oxycarbo nyl ethyl) ph enyl be nzotri azo le, 2,2'-methylene- bis 1,3,3-tetramethyl butyl)-6-benztriazol e-2-yl phenol]; the transesterification product of 2-[3'-te rt-butyl-5'-(2- methoxycarbonyl ethyl) -2'-hyd roxyphenyl]-2 H -benzotriazole with polyethylene glycol 300; [R-CH 2

CH

2 00(CH 2 where R 3'-tert-butyl-4'roxy-5'-2 H-ben zotriazol -2-yl-phenyl.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, as for example 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenyl sal icylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-teributylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hyd roxybenzoate, octadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4, 6-di-tert-butyiphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl ox-cyano-j,f-diphenylacrylate, isooctyl oc-cyano-P43-diphenylacryl ate, methyl oc-carbomethoxycinnamate, methyl c-cyano-P-methyl-p-methoxyci nnamate, butyl c-cyano--m ethyl- p-m ethoxy- cinn am ate, methyl oc-carbomethoxy-pmethoxycinnamate and N-(j3-carbomethoxy-o3-cyanovinyI)-2-methylindoline.

35 Nickel compounds, for example nickel complexes of 2,2'-thio-bis-[4-(1 ,1 ,3,3-tetram ethyl bu tyl) phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-dite rt-butylbenzyl phos phonic acid, nickel complexes of ketoximes, e.g. of 2-hyd roxy-4-m ethylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.

S 2.6. Sterical ly hindered amines, for example bis(2,2, 6,6-tetramethyl-4-piperidyl)sebacate, ~*bi s(2 6, 6-tetram ethyl -4-pi peri dyl)s ucci nate, bis( 1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1 -octyloxy-2,2 ,6,6-tetramethyl-4-piperidyl)sebacate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxy- :::ethyl)-2,2,6,6-tetram ethyl hyd roxypi pe rid in e and succinic acid, the condensate of N,N'bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dicloro- 1, 3,5-triazine, tris(2,2 ,6,6-tetramethyl-4-piperidyl) nitri lotriacetate, tetrakis(2,2, 6,6-tetraethyl4- *'epiperidyl)-1 ,2,3,4-butane-tetracarboxylate, 1,1 ,2-ethanediyl)bis(3,3,5,5-tetras.:methylpiperazinone), 4-be nzoyl -2 6-tetramethyl pipe rid in e, 4-stearyloxy-2,2, 6,6-tetra- *methylpiperidi ne, bis ,2,2 ,6,6-pentam ethyl pipe ridyl) -2-n-butyl -2-(2-hyd Sbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1 ,3,8-triazaspiro[4.5jdecan-2,4-dion, bis(1 octyloxy-2,2, 6,6-tetramethylpiperidyl)sebacate, bis(1 -octyloxy-2,2, 6,6-tetramethylpiperidyl)succi nate, the condensate of N, N'-bis-(2,2, 6,6-tetram ethyl -4-piperi dyl) hexamethylened iamine and 4-m orphol ino-2,6-di chio ro-1, ,3,5-triazi ne, the condensate of 2-chloro-4,6-bis(4-nbutylamino-2,2,6,6-tetramethylpiperidyl)-1 ,3,5-triazine and 1 ,2-bis(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1 ,2,2,6,6-pentamethylpiperidyl)- 1 ,3,5-triazine and 1 ,2-bis-(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7, 9,9-tetramethyl-i ,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1 6-tetramethyl-4-piperi- 3-dodecyl-1 ,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product of N, N'-b is(2,2,6,6-tetram ethyl pipe ri dyl) hexam ethyl ened iam ine and 4cyclohexylamino-2,6-dichloro-1 ,3,5-triazine, a condensation product of 1 ,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1 ,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (GAS Reg. No. [136504-96-61); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid, N-(1 ,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid, 2-undecyl- 36 7,7,9,9-tetramethyl-1 -oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9tetramethyl-2-cycloundecyl-1 -oxa-3,8-diaza-4-oxospiro [4,5ldecane und epichiorohydrin.

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

2.8. 2-(2-Hydroxyphenyl)-1 .3.5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)- 1 ,3,5-triazine, 2-(2-hyd roxy-4-octyloxyphenyl)-4,6-bis (2,4-di methyl phenyl)-1, ,3,5t riazi n e, 2- (2,4-dihydroxyphenyl)-4,6-bis(2,4dimethylphenyl)-1 ,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4methylphenyl)- 1,3, 5-triazine, 2-(2-hyd roxy-4-dodecyloxyphenyl)-4, 6-bis(2,4-di methyiphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2 ,4-dimethylphenyl)-1 hyd roxy-4-(2-hyd roxy-3-butyloxy-propoxy)phenyl]-4, 6-bis(2,4-d im ethyl)-1, ,3,5-triazine, 2- [2-hyd roxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4, 6-bis(2,4-dimethyl)-1 ,3,5-triazi ne, 2- [4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2 ,4-dimethylphenyl)-1 ,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2 ,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4, 6-diphenyl-1 ,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl)-4,6-diphenyl- 1, 3,5-triazine, 2,4, 6-trisll2-hydroxy-4-(3-butoxy-2- 0hyd roxy-propoxy) phenyll- 1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl) -6-phenyl- 0 1 3. Metal deactivators, for example N, N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N, N'-bis(salicyloyl) hydrazine, N, N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1 ,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyloyl)oxalyl dihydrazide, N, N'-bis(salicyloyl)thiopropionyl dihyd razide.

4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilau ryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6- 37 d i-te rt-b utyl-4-m ethyl phenyl) -pentae ryth ritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-te rt-bu tyl-6- methyl pheny) pentae ryth ritol diphosphite, bis(2,4,6-tris(tertbutylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tertbutyiphenyl) 4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8, 1 -tetra-tert-butyl-1 2H-dibenz[d,g]- 1,3,2-dioxaphosphocin, 6-fluoro-2,4,8, 10-tetra-tert-butyl-1 2-methyl-dibenz[d,g]- 1 ,3,2-dioxaphosphocin, bis(2,4-d i-tert- butyl-6-m ethyl phenyl) methylphosph ite, bis(2,4-di-tert- 0:0 butyl-6-m ethyl phenyl) ethyl phosphite.

00066 5. Hydroxylamines, for example, N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, Ndihexadecyihydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-oc- ::*tyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridecyl-nitrone, N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecylaipha-heptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-hep- :*tadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example, dilauryl thiodipropionate or distearyll thiodipropionate.

8. Peroxide scavengers, for example esters of f0-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(3dodecyl mercapto)propionate.

9. Polyamide stabilisers, for example, copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.

Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanu rate, urea derivatives, hydrazine derivatives, amines, polyamides, polyu rethanes, -38alkali 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 tin pyrocatecholate.

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

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

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

0 14. Benzofuranones and indolinones, for example those disclosed in US-A-4325863, US-A- 4338244, US-A-5175312, US-A-5216052, US-A-5252643, DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-ditert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran- 2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tertbutyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2one.

The additional additives, with the exception of the benzofuranones listed under No. 14, are added, for example, in concentrations of from 0.01 to 10%, based on the overall weight of the organic material.

-39- Further preferred compositions comprise not only component and the carrier-bound compounds of the formula I, II, III and/or IV but also further additives, especially phenolic antioxidants, light stabilizers and/or processing stabilizers.

Particularly preferred additives are phenolic antioxidants (section 1 in the list), sterically hindered amines (section 2.6 in the list), phosphites and phosphonites (section 4 in the list) S and peroxide scavengers (section 8 in the list).

*OGG:

Likewise particularly preferred additional additives (stabilizers) are 2-benzofuranones as described, for example, in US-A-4 325 863, US-A-4 338 244, US-A-5 175 312, US-A-5 216 052, US-A-5 252 643, DE-A-4 316 611, DE-A-4 316 622, DE-A-4 316 876, EP-A-0 589 839 and EP-A-0 591 102.

Examples of such 2-benzofuranones are compounds of the formula 14 SR' 1 H in which R'11 is an unsubstituted or substituted, carbocyclic or heterocyclic aromatic ring system;

R'

12 is hydrogen;

R'

14 is hydrogen, alkyl having 1 to 12 carbon atoms, cyclopentyl, cyclohexyl or chlorine; 0

II

R'

13 is as defined for R', 2 or R' 14 or is a radical of the formula -(CH 2 1 0 0 0 O O O II II II -(CH2)C-N(R17)2 -E o 0 0 0 II II II II

-(CH

2 C- -(CH 2 )-C-NR'7-A-0-C-(CH 2 )E 0 0 0 O O O II II II

-(CH

2 )C-N -CH 2

-S-R'

19 -CH(CeHs)-C-OR'16 or-D-E, in which

R'

16 is hydrogen, alkyl having 1 to 18 carbon atoms, alkyl having 2 to 18 carbon atoms which is interrupted by oxygen or sulfur, dialkylaminoalkyl having a total of 3 to 16 carbon atoms, cyclopentyl, cyclohexyl, phenyl or phenyl which is substituted by from 1 to 3 alkyl radicals together having not more than 18 carbon atoms; s is 1 or 2; S the substituents R' 17 independently of one another are hydrogen, alkyl having 1 to 18 0 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl which is substituted by 1 or 2 alkyl radicals together having not more than 16 carbon atoms, a radical of the formula -C 2

H

4 0H, 0

II

-C

2

H

4 -O-CtH 2 t+ or -C 2 H4-O-C-R' 2 0 or together with the nitrogen atom to which they are attached form a piperidine or morpholine radical; t is 1 bis 18; R'2o is hydrogen, alkyl having 1 to 22 carbon atoms or cycloalkyl having 5 to 12 carbon atoms; A is an alkylene having 2 to 22 carbon atoms which is uninterrupted or is interrupted by nitrogen, oxygen or sulfur;

R'

18 is hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, benzyl or phenyl which is substituted by 1 or 2 alkyl radicals together having not more than 16 carbon atoms; R'g is alkyl having 1 to 18 carbon atoms; D is -S02- or -C(R' 2 2 the substituents R' 21 independently of one another are hydrogen or C-C 1 6 alkyl, the two R' 21 substitutents together containing from 1 to 16 carbon atoms, R' 21 also being phenyl or a O O II IIh radical of the formula -(CH 2 or -(CH 2 7 2 in which s, R' 6 and R',7 are as defined above; -41 E is a radical of the formula R' 14 0

R'

12 H in which R' 11

R'

12 and R' 1 4 are as defined above; und

R'

1 5 is hydrogen, alkyl having 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, chlorine or a 0 0 II

II

radical of the formula -CH2-C-OR' 1 6 or -CH--C-N(R' 17 2 in which R' 16 and R' 17 are as defined above, or R' 1 5 together with R' 1 4 forms a tetramethylene radical.

Preferred 2-benzofuranones are those in which R' 13 is hydrogen, alkyl having 1 to 12 carbon 0 O atoms, cyclopentyl, cyclohexyl, chlorine or a radical of the formula -(CH

O

II

S* 72 or in which s, R' 16

R'

17 D and E are as defined above, and

R'

16 is in particular hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl or cyclohexyl.

Further preferred 2-benzofuranones are those in which R' 11 is phenyl or phenyl which is substituted by 1 or 2 alkyl radicals together having not more than 12 carbon atoms; R' 12 is hydrogen; R' 14 is hydrogen or alkyl having 1 to 12 carbon atoms;

O

II

R'

1 3 is hydrogen, alkyl having 1 to 12 carbon atoms, -(CH, 2

O

II

-(CH

2 2 or R' 15 is hydrogen, alkyl having 1 to 20 carbon atoms, O 0 II II -CH2-C-OR'6 or -CH 2 7 or R' 15 together with R' 14 forms a tetramethylene radical, where s, R' 1 6

R'

17 D and E are as defined initially.

-42- Also of particular interest are those 2-benzofuranones in which R' 13 is hydrogen, alkyl having 1 to 12 carbon atoms or R' 1 2 and R' 14 independently of one another are hydrogen or alkyl having 1 to 4 carbon atoms; and R'is is alkyl having 1 to 20 carbon atoms, with D and E being as defined initially.

Likewise of particular interest, finally, are those 2-benzofuranones in which R' 13 is alkyl having 1 to 4 carbon atoms or R' 1 2 and R' 1 4 are hydrogen; and R' 1 i is alkyl having 1 to 4 carbon atoms, cyclopentyl or cyclohexyl, with D being a group -C(R' 2 1 2 and E being a radical of the formula R9 1 *0 in which the substituents

R'

2 i are identical to or different from one another and are each S alkyl having 1 to 4 carbon atoms, and R' 11

R'

1 2

R'

14 and R' 15 are as defined above.

S The quantity of 2-benzofuranones employed additionally can vary within wide limits. There may for example be present in a proportion of from 0.0001 to 5% by weight, preferably from 0.001 to 2% by weight and, in particular, from 0.01 to 2% by weight in the novel compositions.

Incorporation of the carrier-bound compounds of the formula I, 11, 111 and/or IV, and, if appropriate, of further additives into the polymeric organic material is carried out by known methods, for example before or during shaping, or else by applying the dissolved or dispersed carrier-bound compounds of the formula 1, 11, 111 and/or IV to the polymeric organic material, with or without subsequent evaporation of the solvent. The carrier-bond compounds of the formula I, II, III and/or IV can also be added to the materials to be stabilized in the form of a masterbatch containing these carrier-bound compounds in a concentration, for example, of from 2.5 to 25% by weight.

-43- The carrier-bound compounds of the formula I, 11, II1 and/or IV can also be added prior to or during polymerization or prior to crosslinking.

The carrier-bound compounds of the formula I, II, III and/or IV can be incorporated into the material to be stabilized in pure form or encapsulated in waxes, oils or polymers.

The carrier-bound compounds of the formula I, II, III and/or IV can also be sprayed onto the polymer to be stabilized. They are capable of diluting other additives (for example the custo- .0o mary additives indicated above) or melts thereof, and as a consequence can also be foe: sprayed onto the polymer to be stabilized together with these additives. They are added with particular advantage by spray application during the deactivation of the polymerization S catalysts, in which case, for example, the steam which is employed for the deactivation can be used for spraying.

:000 S* In the case of spherically polymerized polyolefins it may, for example, be advantageous to apply the carrier-bound compounds of the formula I, 11, III and/or IV, together if desired with other additives, by spraying.

00o0 S The materials which have been provided with fillers and stabilized in this way can be em- S ployed in a wide variety of forms, for example as films, fibres, tapes, moulding compositions S° or profiles or as binders for surface-coating materials, adhesives or putties.

As already mentioned, the organic materials to be protected are preferably organic polymers, especially synthetic organic polymers. In this context, thermoplastic materials are 0 S: protected with particular advantage, especially polyolefins. A point which should be emphasized in particular here is the outstanding effectiveness of the novel carrier-bound compounds of the formula I, 11, III and/or IV as processing stabilizers (heat stabilizers). For this purpose they are added to the polymer advantageously prior to or during its processing.

However, other polymers, for example elastomers, can also be stabilized against degradation, for example light-induced or thermooxidative degradation. Elastomers can be taken from the above listing of possible organic materials.

-44- A preferred embodiment of the present invention is therefore the use of the carrier-bound compounds of the formula I, II, III and/or IV simultaneously as fillers and stabilizers, especially processing stabilizers (heat stabilizers), for organic materials against oxidative, thermal or light-induced degradation.

The carrier-bound compounds of the formula I, II, III and/or IV are notable for an advantageous colour behaviour, i.e. little discolouration of the organic materials during processing.

The present invention also relates to a method of stabilizing an organic material against oxidative, thermal or light-induced degradation which comprises incorporating in or applying to this material at least one carrier-bound compound of the formula I, II, III and/or IV.

In addition, the present invention also relates to a method of introducing a filler into an organic material, which comprises first coating the filler, prior to its introduction into the organic material, with a compound of the formula I, II, III and/or IV.

S

The examples which follow illustrate the invention in more detail. Parts and percentages are by weight.

Example 1: Preparation of calcium carbonate-bound 3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionic acid of the formula la (compound (101)).

A solution of 2.0 g (7.2 mmol) of 3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionic acid of the formula la in 30 ml of 0.25 N sodium hydroxide solution is added dropwise at 65 0 C to a suspension of 100 g of calcium carbonate in 600 ml of water. The mixture is then stirred for minutes, cooled to room temperature and filtered. The residue is dried at about 65°C in vacuo to constant weight, giving 90 g of calcium carbonate-bound 3-[3,5-di-tert-butyl-4hydroxyphenyl]propionic acid of the formula la (compound The loading concentration is 1.0% by weight.

Example 2: Preparation of calcium carbonate-bound 3-[3-tert-butyl-4-hydroxy-5-methylphenyl]propionic acid of the formula Ib (compound (102)).

A mixture of 400 g of calcium carbonate and 4.0 g of 3-[3-tert-butyl-4-hydroxy-5-methylphenyl]propionic acid is mixed in a mixer at 4000 revolutions/minute until a temperature of 150 0 C is reached. After about 20 minutes the mixture is cooled to room temperature, giving 400 g of calcium carbonate-bound 3-[3-tert-butyl-4-hydroxy-5-methylphenyl]propionic acid of the formula Ib (compound The loading concentration is 1.0% by weight.

Example 3: Preparation of calcium carbonate-bound 3,5-di-tert-butyl-4-hydroxybenzylthioacetic acid of the formula Ic (compound (103)).

Working in analogy to Example 2 and using 400 g of calcium carbonate and 4.0 g of S tert-butyl-4-hydroxybenzylthioacetic acid of the formula Ic gives calcium carbonate-bound 3,5-di-tert-butyl-4-hydroxybenzylthioacetic acid of the formula Ic (compound (103)) with a loading concentration of 1.0% by weight.

Example 4: Preparation of calcium carbonate-bound 3,5-di-tert-butyl-4-hydroxybenzylphos- S* phonic acid of the formula Ila (compound (104)).

Working in analogy to Example 2 and using 400 g of calcium carbonate and 4.0 g of tert-butyl-4-hydroxybenzylphosphonic acid of the formula Ila gives calcium carbonate-bound 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid of the formula Ila (compound (104)) with a S loading concentration of 1.0% by weight.

Example 5: Preparation of calcium carbonate-bound 3-(dodecylthio)propionic acid of the formula Ilia (compound (105)).

Working in analogy to Example 2 and using 400 g of calcium carbonate and 4.0 g of 3-(dodecylthio)propionic acid of the formula Ilia gives calcium carbonate-bound 3-(dodecylthio)propionic acid of the formula Ilia (compound (105)) with a loading concentration of 1.0% by weight.

Example 6: Preparation of calcium carbonate-bound monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate of the formula lib (compound (106)).

-46- Working in analogy to Example 2 and using 400 g of calcium carbonate and 4.0 g of monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate of the formula lib gives calcium carbonate-bound monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate of the formula llb (compound (106)) with a loading concentration of 1.0% by weight.

Example 7: Preparation of calcium carbonate-bound mono(3,3,5,5-tetramethylpiperidyl) succinate of the formula IVa (compound (107)).

Working in analogy to Example 2 and using 400 g of calcium carbonate and 4.0 g of mono- (3,3,5,5-tetramethylpiperidyl) succinate of the formula IVa gives calcium carbonate-bound mono(3,3,5,5-tetramethylpiperidyl) succinate of the formula IVa (compound (107)) with a loading concentration of 1.0% by weight.

Example 8: Preparation of calcium carbonate-bound 2 ,2,6,6-tetramethyl-4-(2,3-epoxypro- °poxy)piperidine of the formula IVg (compound (108)).

Working in analogy to Example 2 and using 400 g of calcium carbonate and 4.0 g of 2 2 ,6,6-tetramethyl-4-(2,3-epoxypropoxy)piperidine of the formula IVg gives calcium carbonate-bound 2 2 6 ,6-tetramethyl-4-(2,3-epoxypropoxy)piperidine of the formula IVg (compound (108)) with a loading concentration of 1.0% by weight.

Example 9: Preparation of titanium oxide-bound 1,2,2,6,6-pentamethyl-4-(2,3-epoxypropoxy)piperidine of the formula IVh (compound (109)).

g (118 mmol) of titanium oxide (Tiosorb"UF01, Tioxide Specialities Ltd., England) and g (2.2 mmol) of 1, 2 2 6 ,6-pentamethyl-4-(2,3-epoxypropoxy)piperidine [EP-A-0 634 449, Example Al] are suspended in 100 ml of methylene chloride and the suspension is then concentrated under vacuum on a rotary evaporator. The residue is left to stand for 6 hours at 200°C. The product is then cooled and subjected twice to extraction with n-hexane, giving titanium oxide-bound 1, 2 2 6 ,6-pentamethyl-4-(2,3-epoxypropoxy)piperidine of the formula IVh (compound (109)) with a loading concentration of 4.0% by weight. This value is determined by means of nitrogen determination by the Kjeldahl method.

-47- Example 10: Preparation of silcon oxide-bound 1,2,2,6,6-pentamethyl-4-(2,3-epoxypropoxy)piperidine of the formula IVh (compound (110)).

g (158 mmol) of silicon oxide (Aerosil"380, Degussa, Germany) and 0.5 g (2.2 mmol) of 1,2,2,6,6-pentamethyl-4-(2,3-epoxypropoxy)piperidine [EP-A-0 634 449, Example Al] are suspended in 100 ml of methylene chloride and the suspension is then concentrated under vacuum on a rotary evaporator. The residue is left to stand for 5 hours at 200°C, giving silicon oxide-bound 1,2,2,6,6-pentamethyl-4-(2,3-epoxypropoxy)piperidine of the formula IVh (compound (110)) with a loading concentration of 5.2% by weight. The measurement of the nitrogen content of the product by the Kjeldahl method gives a value of 0.39% by weight.

For checking purposes, the product is additionally subjected to extraction with boiling n-hexane for 18 hours in a Soxhlet apparatus and the product-containing extract is then dried.

Renewed nitrogen determination of this product by the Kjeldahl method gives a value of 0.39% by weight. Consequently, the stabilizer (compound of the formula IVh) cannot be 0. removed from the silicon oxide by extraction with n-hexane.

Example 11: Preparation of silicon oxide-bound 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-(2,3epoxypropoxy)piperidine of the formula IVi (compound (111)).

@0 Working in analogy to Example 10 and using 9.5 g of silicon oxide and 0.5 g of 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-(2,3-epoxypropoxy)piperidine of the formula IVi [EP-A-0 634 449, Example A2] gives silicon oxide-bound 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-(2,3-epoxypropoxy)piperidine of the formula IVi (compound (111)) with a loading S concentration of 5.2% by weight.

Example 12: Preparation of silicon oxide-bound 1-octyloxy-2,2,6,6-tetramethyl-4-(2,3-epoxypropoxy)piperidine of the formula IVk (compound (112)).

Working in analogy to Example 10 and using 9.5 g of silicon oxide and 0.5 g of 1-octyloxy- 2,2,6,6-tetramethyl-4-(2,3-epoxypropoxy)piperidine of the formula IVk [EP-A-0 634 449, Example A3] gives silicon oxide-bound 1-octyloxy-2,2,6,6-tetramethyl-4-(2,3-epoxypropoxy)piperidine of the formula Ivk fixed to silicon oxide (compound (112)) with a loading concentration of 5.2% by weight.

-48- Example 13: Preparation of silicon oxide-bound 1-benzyl-2,2,6,6-tetramethyl-4-(2,3-epoxypropoxy)piperidine of the formula IVm (compound (113)).

Working in analogy to Example 10 and using 9.5 g of silicon oxide and 0.5 g of 1 -benzyl- 2,2,6,6-tetramethyl-4-(2,3-epoxypropoxy)piperidine of the formula IVm [EP-A-0 634 449, Example A4] gives silicon oxide-bound 1-benzyl-2,2,6,6-tetramethyl-4-(2,3-epoxypropoxy)piperidine of the formula IVm fixed to silicon oxide (compound (113)) with a loading concentration of 5.2% by weight.

S Example 14: Preparation of calcium carbonate-bound N-[4-(2,2,6,6-tetramethyl)piperidyl]aminoacetic acid of the formula IVf (compound (114)).

00 Working in analogy to Example 2 and using 400 g of calcium carbonate and 4.0 g of N-[4- (2,2,6,6-tetramethyl)piperidyl]aminoacetic acid of the formula IVf Reg. No. 71866-13-2] gives calcium carbonate-bound N-[4-(2,2,6,6-tetramethyl)piperidyl]aminoacetic acid of the formula IVf fixed to calcium carbonate (compound (114)) with a loading concentration of by weight.

Example 15: Preparation of calcium carbonate-bound mono(3,3,4,5,5-pentamethylpiperidyl) succinate of the formula IVb (compound (115)).

00

S

a) Working in analogy to Example 2 and using 400 g of calcium carbonate and 4.0 g of mono(3,3,4,5,5-pentamethylpiperidyl) succinate of the formula IVb [Example 15b] gives calcium carbonate-bound mono(3,3,4,5,5-pentamethylpiperidyl) succinate of the formula IVb f: (compound (115)) with a loading concentration of 1.0% by weight.

b) A mixture of 85.5 g (0.50 mol) of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 50 g (0.50 mol) of succinic anhydride and 500 ml of xylene is boiled under reflux for one hour. The reaction mixture is subsequently poured into 3 litres of n-hexane. The product is filtered, and crystallization of the residue from xylene gives 125 g (92 of mono(3,3,4,5,5-pentamethylpiperidyl) succinate of the formula IVb, m.p. 163°C. Analysis calculated: C 61.97; H 9.29; N 5.16%. found: C 61.92; H 9.43; N 5.10%.

-49- Example 16: Preparation of calcium carbonate-bound mono(3,3,5,5-tetramethylpiperidyl)succinamide of the formula IVc (compound (116)).

a) Working in analogy to Example 2 and using 400 g of calcium carbonate and d 4,0 g of mono(3,3,5,5-tetramethylpiperidyl)succinamide of the formula IVc [Example 16b] gives calcium carbonate-bound mono(3,3,5,5-tetramethylpiperidyl)succinamide of the formula IVc (compound (116)) with a loading concentration of 1.0% by weight.

b) A mixture of 48 g (0.30 mol) of 4-amino-1,2,2,6,6-tetramethylpiperidine, 30 g (0.30mol) of succinic anhydride and 1000 ml of xylene is boiled under reflux for 6 hours. The reaction mixture is subsequently poured into 3 litres of n-hexane. The reaction mixture is subsequently cooled and the precipitated product is filtered. Crystallization of the residue from S acetone/water gives 64 g (83% of mono(3,3,5,5-tetramethylpiperidyl)succinamide of the formula IVc, m.p. 322 0 C. Analysis calculated: C 60.91; H 9.44; N 10.93%. found: C 60.47; H 9.50; N 10.86%.

Example 17: Preparation of calcium carbonate-bound mono(3,3,4,5,5-pentamethylpiperidyl)succinamide of the formula IVd (compound (117)).

a) Working in analogy to Example 2 and using 400 g of calcium carbonate and 4,0 g of mono(3,3,4,5,5-pentamethylpiperidyl)succinamide of the formula IVd [Example 17b] gives calcium carbonate-bound mono(3,3,4,5,5-pentamethylpiperidyl)succinamide of the formula IVd (compound (117)) with a loading concentration of 1.0% by weight.

*see b) Mono(3,3,4,5,5-pentamethylpiperidyl)succinamide of the formula IVd is prepared in analogy to Example 16b using 4-amino-1,2,2,6,6-pentamethylpiperidine instead of 4-amino- 2,2,6,6-tetramethylpiperidine.

Example 18: Preparation of calcium carbonate-bound 2,2,6,6-tetramethyl-4-piperidyloxyacetic acid of the formula IVe (compound (118)).

Working in analogy to Example 2 and using 400 g of calcium carbonate and 4.0 g of 2,2,6,6-tetramethyl-4-piperidyloxyacetic acid of the formula IVe gives calcium carbonatebound 2,2,6,6-tetramethyl-4-piperidyloxyacetic acid of the formula IVd (compound (118)) with a loading concentration of 1.0% by weight.

Example 19: Preparation of calcium carbonate-bound mono(3,3,5,5-tetramethylpiperidyl)dodec-2-enylsuccinamide of the formula IVn (compound (119)).

a) Working in analogy to Example 2 and using 400 g of calcium carbonate and 4,0 g of mono(3,3,5,5-tetramethylpiperidyl)dodec-2-enylsuccinamide of the formula IVn [Example 19b] gives calcium carbonate-bound mono(3,3,5,5-tetramethylpiperidyl)dodec-2-enylsuccinamide of the formula IVn (compound (119)) with a loading concentration of 1.0% by weight.

b) A mixture of 11.7 g (75 mmol) of 4-amino-1,2,2,6,6-tetramethylpiperidine, 20 g (75 mmol) S of dodec-2-enylsuccinic anhydride [Fluka 45346] and 250 ml of xylene is boiled under reflux for 6 hours. The reaction mixture is subsequently cooled and is concentrated under vacuum in a rotary evaporator. Crystallization of the residue from methanol/acetonitrile gives 30 g (95% of mono(3,3,5,5-tetramethylpiperidyl)dodec-2-enylsuccinamide of the formula IVn, m.p. 1820C. Analysis calculated: C 71.05; H 10.97; N 6.63%. found: C 69.89; H 10.89; N 6.60%.

Example 20: Preparation of talc-bound 3-(dodecylthio)propionic acid of the formula Ilia S (compound 120)).

g of talc (Luzenac e are added to a solution of 0.5 g of 3-(dodecylthio)propionic acid of the formula Illa in 200 ml of hexane. The mixture is subsequently concentrated under vacuum in a rotary evaporator, giving 50.5 g of talc-bound 3-(dodecylthio)propionic acid of the formula Ila (compound The loading concentration is 1.0% by weight.

Example 21: Incorporation of calcium carbonate into polypropylene (dispersibility test).

parts by weight of polypropylene granules (Propathene" GYM 45) are mixed with parts by weight of calcium carbonate and, respectively, with 20 parts by weight of the novel calcium carbonate-bound compounds from Examples 1 to 8 at 230°C in a Gottfert Etrusiometer. The propylene tapes obtained from the extrusion are pressed at 1900C for 2 minutes -51 to give 0.5 mm thick films. The dispersion of the calcium carbonate (filler) in the films is then assessed visually in accordance with the following key: 1 very poor; 2 poor; 3 average; 4 average-good; 5 good; 6 very good. The results are compiled in Table 1.

Table 1: Filler Dispersion parts of calcium carbonate 3 (average) parts of compound (105) 6 (very good) parts of compound (106) 5 (good)

S

0O e 0 0*0e e 0 0

S

0 00 S 0S0 0

S

0000

S

*000 00 50 S *0tO

S

*5 S 0 *r 0 SO. 0

S

0000 0 0055 -52-

C

0 6@ C 0 C C *0

C

0000 0O a *0&e *0CC C C 00 C

C

00 Example 22: Stabilization of polypropylene, oven ageing test and exposure to light test.

parts by weight of the novel carrier-bound compounds from Examples 1 to 20 are mixed with 60 parts by weight of polypropylene powder ("Profax 6501) under nitrogen for 6 minutes at 2300 C in a Brabender plastograph. The mixture is subsequently compression moulded at 230 0 C to give 1.0 mm thick plates from which 45 x 17 mm test specimens are punched. Some of these test specimens are then aged in a conventional oven at 1350C. A measurement is made of the time which lapses before the appearance of a physical, locally restricted discolouration in the test specimens. The longer this time, the more effective the stabilizer. The results are compiled in Table 2.

Table 2: Oven ageing test at 1350C Filler Days to decomposition parts of calcium carbonate 1 40 parts of compound (102) 9 parts of compound (107) 9 parts of compound (108) 9 The other test specimens are subjected to an exposure to light test (Atlas weatherometer type WOM Ci 65, black panel temprature 630C). The gloss and the surface roughness of these specimens is then determined, the gloss is measured using a deflector. The yardstick used for measuring the gloss of the surface is the reflectometer value (ROM). Its magnitude is determined by the proportion to which the surface contributes, on the basis of its reflection properties, to the formation of the impression of gloss. The reflectometer value is therefore the optical parameter for the gloss and thus also for the degree of decomposition of a surface. The greater the value, the better the sample surface. To determine the surface roughness (Ra) the test specimen is scanned with a measurement needle at a certain length in order to obtain a measured profile (length, high points, low points). Ra denotes the arithmetic mean of the absolute contributions of all profile ordinates within the overall section measured after filtering out deviations in form and coarse components of the waviness.

The higher the value, the poorer the sample surface. The results are compiled in Table 3.

-53- Table 3: Exposure to light test Gloss (ROM) Surface roughness (Ra) Filler after hours after hours 0 250 400 500 0 250 400 500 parts of calcium carbonate 74 40 17 13 0.11 0.44 0.93 1.22 parts of compound (107) 70 62 61 61 0.12 0.16 0.16 0.18 parts of compound (108) 72 68 67 67 0.12 0.14 0.15 0.15 Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.

a.

a a a a a a

S

Claims

1. An oxide-, hydroxide-, silicate- or carbonate-based filler coated with a compound of the formula 1, 11, 111 and/or IV HOII (R 2 x p--a II R H 3C D -ZI l ((lV H 3C CH 3 CH 3 in which R, is 0 1 -Cl 8 alkyl, C 5 -C 12 cycloalkyl, phenyl or C 7 -Cgphenylalkyl, R 2 is 0 1 -C, 8 alkyl, C 5 -C 12 cycloalkyl, phenyl or C 7 -Cgphenylalkyl, R 4 is hydrogen, Cl-C 20 akyl, naphthyl or phenyl which is unsubstitued or is substituted by 0 1 -C 4 alkyl; ammonium or M r 55 R 5 is hydrogen, 0 1 -C 2 oalkyI, naphthyl or phenyl which is unsubstituted or is substituted by C 1 ,-C 4 alkyl; ammonium or r r R 6 is hydrogen, 0 1 -C 18 alkyl, C 5 -C 12 cycloalky, C 7 -Cgphenylalkyl, ammonium orMr r R-1 is C 1 -C 18 alkyl, phenyl which is unsubstituted or is substituted by C 1 .(0 4 alkyI or -(CH 2 COR,, Rf3 is C-,-C 8 alkyl, R 9 is hydrogen, CI-C 8 alkyI, OH, NO, -01H 2 CN, Ci-Q 18 alkoxy, C6-C-jp ,ycloalkyloxy, C3-Clalkenyl, 0 3 -Clalkynyl, Cj-C 8 acy[, C7-Cgphenylalky; which is unsub';tituted or is substituted on the pheny! ring by CI-C~alkyl, Rio is C-C0R CH--CH--CH or -X j-COOR 6 R 11 is hydrogen or 0 1 -C,,alkyI, Rip is 0 1 -C 18 aikyi or C 2 -Cl 4 alkenyl, R 1 3 is hydrogen or Cl-C 4 alkyI, M is an r-valent metal cationion, X, is a direct bond, Cl-C 8 alkylene, C 2 -C 8 alkylene which is interrupted by oxygen or sulfur; -CHi---CH- or HO-0 ,where R, und R 2 are as defined,

4. R8I CH 3 R2 3 ::X 2 is oxygen or -NH-, X 3 is Cl-O 6 alkylene, X 4 is oxygen or -NR 11 X 5 is a direct bond, Cl-C 8 alkylene, C2-C 8 alkenylene, CH-R 12 Rz 56 -P-P 3 or -P-R6, 0000 *as.* S S. 0 S S. S S S S *5S5 S S *0 9* S.. S S S S 5 5**S 55*55* X 6 is C 1 -C, 8 alkylene, C2-Cl 8 alkenylene, 02-Ol8alkylene which is interrupted by oxygen or* sulfur; or is phenylene, m is 0, 1 or 2, n is an integer in the range from 1 to 6, p is 1 or 2, q is I or 2, is 1,2 or3, and if r! is F4 3 is hydrogen., -01-20lkYCf Cioalkyl, phanyi which is unsubstituted or is substitutedi hY Ci-C 4 alkyl-, a monovalent radical of a hexos(&, a monovalent radical of a. hexitol; and, if X: is oxygen, R 3 isadditionally amoimo or, r if n is 2, R 3 is C 2 -Cl 2 alkylene, C 4 -Cl 2 alkylene which is interrupted by oxygen or sulfur; a divalent radical of a hexose or a divalent radical or a hexitol, or if n is 3, R 3 is -H-CH trivalent radical of a hexose or a trivalent radical of a hexitol, or if n is 4, R 3 is 04-ClOalkanetetrayl, a tetravalent radical of a hexose or a tetravalent radical of a 'hexitol, or 57 if n is R 3 is a pentavalent radical of a hexose or a pentavalent radical or a hexitol, or if n is 6 -CH 2 OHr- R 3 is CHi--CH--O--CH-C;-;HT- or a hexavalent radical of a hexitol. -OH 2 2. A coated filler according to claim 1, wherein the compound is-of the formula 1, 11 or 1ll. 3. A coated'filler according to'claim 1, wherein R, is CI-C 12 alkyl, C 5 -C1cycloalkyi, phenyl or C 7 -Cgphenylalkyl, R 2 is 0 1 -Cl 2 alkyt, C 5 ,-C 8 cycloalkyl, phenyl or C 7 -Cgphenylalkyl, R 4 is hydrogen, Cl-Cl 2 alkyl, phenyl which is unsubstituted or is substituted by C 1 -0 4 alkyl; 6:6 ammonium orM 6666 r 66 66 R 5 is hydrogen, Cl-Cl 2 alkyl, phenyl which is unsubstituted or is substituted by C 1 -C 4 alkyl; ammonium or Mr

66.. r R 6 is hydrogen, Cl-Cl 2 alkyl, C 5 -C 8 cycloalkyl, 0 7 -Cgphenylalkyl, ammonium or R 7 is C 2 -C, 6 alkyl, phenyl which is unsubstituted or is substituted by Cl-C 4 alkyl; or is 666666R (CH 2 q CR 6 R 8 is Cl-C 4 alkyl, M is an alkali metal, alkaline earth metal or aluminium, 58 X, is a direct bond, Cl-C 6 alkylene, 0 2 -C 6 alkylene which is interrupted by oxygen or sulfur; or -CHF-CH- I R8 or HOC-Cii- where R, and R 2 are as defined I -O-CHI 3 Us.. 9* U S U U U *U S S a U S U Sass U U U U U a. a S S above, Xis oxygen or -NH-, X 3 is 0 1 -C 5 alkylene, mn is 1 or 2, n is an integer from the range from 1 to 4, p is 1 or 2, q isi1 or 2, r is 1, 2 or.3, and if n 1, R 3 is hydrogen, Cl'C, 8 alkyl, C 5 -C 8 cycloalkyl, phenyl which is unsubstituted or is substituted Mr+ by Cl-C 4 alkyl; and if X 2 is oxygen, R 3 is additionally ammonium or or r if n =2, R 3 is C 2 -Cl 0 alkylene, C 4 -Cl 0 alkylene which is interrupted by oxygen or sulfur, or if n 3, if n 4, 04-C~alkanetetrayl. 59 4. A coated filler according to claim 1, wherein R, is Cl-CloalkyI, 0 5 -C 6 cycloalkyl, phenyl or benzyl, R 2 is 0 1 -Cl 0 alkyI, C 5 -C 6 cycloalkyl, phenyl or benzyl, R 4 is hydrogen, Cl-CloalkyI, phenyl, ammonium or M r R 5 is hydrogen, CI-C 10 alkyI, phenyl, ammonium or r R is hydrogen, 0 1 -Cloalkyl, C 5 -C 6 cycloalkyl, benzyl, ammonium or Mr R 7 is C 4 -C 14 alkyl, phenyl or -(CH 2 )qj--CO 2 R 6 -R 8 is methyl, M is an alkali metal, alkaline earth metal or aluminium, X, is a direct bond, Cl-C 4 alkylene, C 2 -C 6 alkylene which is interrupted by sulfur; or is *or HO /0 L C-O;H- ,where Rand R 2 are as defined R 8 2 above, X2is oxygen, X 3 is 0 1 -C 4 alkylene, m misl1or 2, n is a integer from the range from 1 to 4, p is 2, is 2, r is 1,2 or3, and if n 1, 60 a a a. a a a a a. a a a a a a I a a a a a a a a. a a a a a R 3 is hydrogen, C 1 -C 12 alkyl, C 5 -C 6 cycloalkyl, phenyl, ammonium or H or r if n= 2, R 3 is C 2 -C 8 alkylene, C 4 -Cl 0 alkylene which is interrupted by oxygen, or if n =3, R 3 is -H 2 ,or if n 4, R 3 is -CH2---C~ S. A coated filler according to claim 1, wherein R, is tert-butyl, R 2 is C 1 -C 4 alkyl and is ortho to the OH group, and M is 1. 6. A coated filler according to claim 1, wherein R 9 is hydrogen, methyl, C 8 -0 12 -alkoxy, cyclohexyloxy or benzyl. 7. A coated filler according to claim 1, wherein R 6 is hydrogen, Cl-Cloalkyl, Cs-Crcycloalkyl, benzyl, ammonium or Mr R 9 is hydrogen, Cl-C 4 alkyl, 0% OH, NO, C 4 -Cl 8 alkoxy, C 5 -C 7 cycloalkoxy, 0 2 -C 6 acyl, C 7 -C 9 -phenylalkyl which is unsubstituted or is substituted on the phenyl ring by Cl-C 4 alkyl, 61 0 0 Rio is -C-X-COOR 6 1 -CHI-CH-CH 2 or -X--COOR 6 R, I is hydrogen or C 1 -C 12 alkyI, R 12 is Cl-Cl 2 alkyI or C 6 -Cl 4 alkenyI, R 13 is hydrogen or methyl, M is a alkali metal or an alkaline earth metal, X 4 is oxygen or X 5 is a direct bond, Cl-C 6 alkylene, C 2 -C 6 alkenylene, CH-R 12 F R 3 or R 1 F 3 X 6 is Cl-Cl 2 alkylene, C 2 -Cl 2 alkenylene, C 2 -Cl 2 alkylene which is interrupted by oxyen; or is phenylene, and s. 6: a. r s1 r2 S. A coated filler according to claim 1, wherein R 6 is hydrogen, Cl-C 8 alkyl, cyclohexyl or M r a R 9 is hydrogen, Cl-C 4 alkyl, C 4 -Cl 8 alkoxy, CS-C 7 cycloalkoxy, C 2 -C 6 acyl or 0 7 -Cgphenylalkyl, 0I 0 Rio is -C-X--C;00R 6 -CHi---CH--CH 2 or -X C003 6 ee~ R 11 is hydrogen or Cl-Caalkyl, Osseo: R 12 is CI-C 8 alkyl or C 6 -Cl 4 alkenyl, R 13 is hydrogen or methyl, M is an alkali metal or alkaline earth metal, X 4 is oxygen or X 5 is a direct bond, 0 1 -C 6 alkylene, PHR 2 Rl 13 3 o 62 -P- 1 3 dlarstelt, X 6 is Cl-C 8 alkylene, C 2 -C 8 alkenylene, 0 2 -C 8 alkenylene which is interrupted by oxygen; or is phenylene, and r isi1 or 2. 9. A coated filler according to claim 1, wherein R, is CI-C 6 alkyl, cyclohexyl or phenyl, R 2 is Cl-C 6 alkyl, cyclohexyl or phenyl and is ortho to the OH group, R 3 is hydrogen, Cl-C 8 alkyl, cyclohexyl or M r R 4 is hydrogen, CI-C 8 aikyl orM r R 5 is hydrogen, Cl-C 8 alkyl or ~L r Mr+ R 6 is hydrogen, Cl-C 8 alkyl, cyclohexyl orM R 7 is C 8 -C 14 alkyl or -(CH 2 C 2 R 6 R 8 is methyl, V V R 9 is hydrogen, Cl-C 4 alkyl, C 4 -Cl 2 alkoxy, C5-C7cycloalkoxy, acetyl or C 7 -Cgphenylalkyl, 0 0 R 1 0 is ',-A5COOR 6 CH-CH-CH 2 or -X COOR 6 R 11 is hydrogen or 0 1 -C 4 alkyI, R 12 is CO-Cl 4 alkenyl, R 13 is hydrogen or methyl, M is an alkali metal or alkaline earth metal, X1 is 02-C 4 alkylene, C 2 -C 4 alkylene which is interrupted by sulfur; or isI R8 63 X 2 is oxygen, X 3 is Cl-C 4 alkylene, X 4 is oxygen or X 5 is a direct bond, Cl-C 4 alkylene CH 1 3 or X 6 is C 1 -C 4 alkylene or phenylene, mn is 1 or 2, n is 1, p is2, q is 2, and r risl1or 2. A coated filler according to claim 1, wherein R, is tert-butyl, R 2 is C 1 -C 4 alkyl and is ortho to an OH group, R 3 is hydrogen or Cl-C 4 alkyl, 6 R 4 is hydrogen, Cl-C 4 alkyl orMr 6 r R 5 is hydrogen, Cl-C 4 alkyI or Mr r R 6 is hydrogen, R 7 is C 10 -Cl 2 alkyl, R 9 is hydrogen, methyl, 0 8 -Cl 2 alkoxy, cyclohexyloxy or benzyl, 0 0 R 1 0 is -A-COOR 6 -CH--CH-CH 2 or -XCOOR 6 R 11 is hydrogen, R 12 is ClO-C 12 alkenyl, -64- M is calcium, X, is ethylene or ethylene which is interrupted by sulfur, X 2 is oxygen, X 3 is methylene, X 4 is oxygen or -NR 11 X 5 is ethylene or CH-R X 6 is methylene, m is 1, n is 1, p is 2, and r is2. 11. A coated filler according to claim 1, wherein the carrier is aluminium oxide, magnesium oxide, titanium oxide, silicon oxide, talc, calcium carbonate or dolomite. 12. A coated filler according to claim 1, wherein the compound of the formula I, II, III and/or IV, relative to the weight of the filler, is present in a quantity of from 0.01 to 10% by weight. 13. A composition comprising a) an organic material which is subject to oxidative, thermal or light-induced degradation and b) at least one coated filler according to claim 1. 14. A composition according to claim 13, wherein component is present in a quantity of from 1 to 50% based on the weight of component *0 A composition according to claim 13, comprising further additives in addition to the components and 16. A composition according to claim 15, comprising as further additives phenolic antioxi- dants, light stabilizers and/or processing stabilizers. 17. A composition according to claim 15, comprising as further additive at least one com- pound from the class of the 2-benzofuranones. 18. A composition according to claim 13, comprising as component natural, semisynthe- tic or synthetic polymers. 19. A composition according to claim 13, comprising as component a natural or semi- synthetic polymer for papermaking. A composition according to claim 13, comprising as component thermoplastic polymers. 21. A composition according to claim 13, comprising as component a polyolefin. 22. A composition according to claim 13, comprising as component polyethylene or polypropylene. 0000 0000 ~23. A composition according to claim 13, comprising as component asphalt, bitumen or a bituminous material. 0000 0000 24. Use of coated filler according to claim 1 as stabilizer for organic materials against oxidative, thermal or light-induced degradation. Use according to claim 24 as processing stabilizer (heat stabilizer) in thermoplastic polymers. 0 z 26. A method of stabilizing an organic material against oxidative, thermal or light-induced degradation, which comprises incorporating in or applying to this material at least one coated filler as defined in claim 1. 27. A method of introducing an oxide-, hydroxide-, silicate- or carbonate-based filler into an organic material, which comprises first coating the filler, prior to its introduction into the organic material, with a compound of the formula I, II, III and/or IV as defined in claim 1. 66 28. A coated filler and compositions containing the same substantially as hereinbefore described with reference to the Examples. DATED this 12th day of November

1999. CIBA SPECIALTY CHEMICALS HOLDING INC. By Its Patent Attorneys DAVIES COLLISON CAVE be 6 0..0. S