BE1011643A3 - Composition stabilized, mixture of stabilizers and method for stabilizing an organic matter. - Google Patents

Abstract

The invention relates to a composition stabilized by a mixture of stabilizers against degradation caused by light, heat or oxidation. The composition comprises an organic material to be stabilized, such as a natural or synthetic polymer, for example a polyolefin, and at least one compound with a benzofuran-2-one structure, at least one compound from the class of organic phosphites and phosphonites, at least one compound from the class of phenolic antioxidants and at least one compound from the class of hindered amines. Areas of application: stabilizers for plastics.

Description

       

    <Desc / Clms Page number 1>
 



   "Stabilized composition, mixture of stabilizers, and method for stabilizing organic matter"
The present invention relates to compositions comprising an organic material sensitive to degradation caused by oxidation, heat or light and, as stabilizers, at least one compound with a structure of benzofuran-2-one, at least one compound of the phosphite type. or phosphonite, at least one compound of the phenolic antioxidant type and at least one compound of the sterically hindered amine type, and the use of these stabilizers to stabilize organic materials against degradation caused by oxidation, heat or light.



   The use of compounds with a benzofuran-2-one structure as stabilizers for organic polymers is known, for example, from U.S. patents.



    NO 4 325 863.4 388 244.5 175 312.5 252 643.5 216 052, 5 369 159.5 488 117.5 356 966.5 367 008.5 428 162, 5 428 177 or 5 516 920.



   Organic phosphites, phosphonites and phosphoramides are known in the art as co-stabilizers, secondary antioxidants and processing stabilizers, among others for polyolefins. Examples of these known phosphite stabilizers can be found in Plastics Additives Handbook, edited by R. Gâchter / H. Müller, 3rd edition, page 47, Hanser, Munich 1990.



   US Pat. No. 4,360,617 teaches that mixtures of stabilizers comprising symmetric triaryl phosphites and certain phenolic antioxidants are particularly suitable for the protection of certain organic materials, such as polyurethane, polyacrylonitrile, polyamide 12 and polystyrene, against degradation caused by oxidation, heat or light.



   Sterically hindered amines, including particular compounds containing 2,2, 6,6-tetra- groups

  <Desc / Clms Page number 2>

 methylpiperidyl, are known as sterically hindered amine type light stabilizers (SLAES).



   The known stabilizers do not in all respects meet the great requirements which a stabilizer must satisfy, in particular with regard to the shelf life during storage, absorption of water, sensitivity to hydrolysis, stabilization during setting. work, the chromatic properties, the volatility, the migration behavior, the compatibility and the improvement of the protection against light. There is therefore always a need for effective stabilizers for organic materials which are sensitive to degradation caused by oxidation, heat and / or light.



   It has now been discovered that a mixture of stabilizers comprising at least one compound with a benzofuran-2-one structure, at least one compound of the phosphite or organic phosphonite type, at least one compound of the phenolic antioxidant type and at least one compound of the type hindered amine is particularly suitable as a stabilizer for organic materials which are susceptible to degradation caused by oxidation, heat or light.



   The present invention therefore provides compositions comprising a) an organic material which is sensitive to degradation caused by oxidation, heat or light, b) at least one compound with a structure of benzofuran-2-one, c) at least a compound from the class of organic phosphites and phosphonites, d) at least one compound from the class of phenolic antioxidants, and e) at least one compound from the class of sterically hindered amines.



   Compositions which are of interest include those containing, as component (b), a compound of the formula

  <Desc / Clms Page number 3>

 
 EMI3.1
 in which, if n is 1,
R1 is a naphthyl, phenanthryl, anthryl group, 5,6, 7,8-tetrahydro-2-naphthyl, 5,6, 7, 8-tetrahydro-1-naphthyl, thienyl, benzo [b] thienyl, naphtho [2, 3-b] thienyl, thianthenyl, dibenzofuryl, chloromenyl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, iso-indolyl, indolyl, indazinyl, purinyl, quinolyl, quinolyl quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, ss-carbolinyl, phenanthridinyl, acridinyl, peridinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl,

   furazanyl, biphenylyl, terphenylyl, fluorenyl or phenoxazinyl, unsubstituted or substituted by
 EMI3.2
 one or more C 1 -C 4 alkyl, C 1 -C 4 alkoxy C 1 -C alkylthio, hydroxyl, halo, amino, C alkylamino <-C., Phenylamino or di (C1-C4 alkyl) amino, or else R1 is a group of formula II
 EMI3.3
 and, if n is 2, R. is a phenylene or naphthylene group unsubstituted or substituted by one or more C1-C4 alkyl or hydroxyl groups; or is-R-X-R-,
R2, R3, R4 and Re are each, independently of the others, hydrogen, chlorine or a hydroxyl group, C1-C25 alkyl, phenylC7-C9 alkyl;

   unsubstituted phenyl

  <Desc / Clms Page number 4>

 or substituted by one or more C1-C4 alkyl groups; C5-C8 cycloalkyl unsubstituted or substituted by one or more C1-C4 alkyl groups; Cl-Cl8 'alkoxy
 EMI4.1
 C1-C18 alkylthio C1-C4'alkylamino (C1-C4 alkyl) amino, C.sub.1 -alkanoyloxy, C1-C25 alkanoyiamino, C.sub.C alkenoyloxy, C.sub.C-alkanoyioxy which is interrupted by by oxygen, sulfur or NR. ; cycloalkyl-11, carbonyloxy C e carbonyloxy Cg-Cq, benzoyioxy or benzoyloxy substituted by one or more alkyl groups C1-C12;

   or the radicals R2 and R3 or the radicals R3 and R4 or the radicals R4 roams, with the carbon atoms to which they are attached, form a joined benzene nucleus, R4 can also be - (CH) -CORou- (CH) OH or, if R, R and R6 are each hydrogen, R4 may also be a group of formula III
 EMI4.2
 where R is as defined above for n = 1,
R6 is hydrogen or a group of formula IV
 EMI4.3
 where R4 is not a group of formula III and R1 is as defined above for n = 1,
R7, R8, R9, R10 and R11 are each, independently of the others, hydrogen, halogen or a hydroxyl group,
 EMI4.4
 C1-C251 alkyl C-Cc alkyl interrupted by oxygen, sulfur or) N-R14; C, -C25 alkoxy 14-2 alkoxy, C-CE alkoxy interrupted by oxygen, sulfur or N-R ..;

   alkylthioenC.-Cc, alkenylenC-CE, alkenyloxyenC-CE, 1 25, C3-C25 alc'nyl, 3-c25 '

  <Desc / Clms Page number 5>

 C3-C25 alkynyl, C3-C25 alkynyloxy, C7-C9 phenylalkyl, C7-C9 phenylalkoxy; phenyl unsubstituted or substituted by one or more C1-C4 alkyl groups; phenoxy unsubstituted or substituted by one or more C1-C4 alkyl groups; C5-C8 cycloalkyl unsubstituted or substituted by one or more C1-C4 alkyl groups; C 1-6 cycloalkoxy unsubstituted or substituted by one or more C 1-4 alkyl groups; C1-C4 alkylamino di (C1-C4 alkyl) amino, C 1-6 alkanoyl, alkanoyl
 EMI5.1
 C3-C25 interrupted by oxygen, sulfur or::;

   N-R14; 25. 11 14; C alkanoyloxy <-Ce, C3-C25 alkanoyioxy interrupted by oxygen, sulfur or N-R ..; alcanoyiamino enC <-Ce, C-CE alkenoyl, C-CE alkenoyy interrupted by 2., C3-C25 alk'noyl oxygen, sulfur or # N-R14; C3-C25 alkenoyloxy, C-CE alkenoyloxy interrupted by oxygen, sulfur or N-R14; C6-Cn cycloalkylcarbonyl, C6-C9 cycloalkylcarbonyloxy; unsubstituted or substituted benzoyl
 EMI5.2
 by one or more C-C alkyl groups <;

   benzoyioxy unsubstituted or substituted by one or more groups
 EMI5.3
 R 0 1 118 Il 1 Il 1 1 CC alkyl; -0-CC-Rg or-0-CCOR, a 1 ky 1 een C 1-C 1 2 i OCCR5 o uOCCOR23 Z Rg HR m 19 H Fi = or else , in formula II, the radicals R7 and Rg or the radicals Rg and Roll, with the carbon atoms to which they are attached, form a joined benzene ring, R12 and R13 are each, independently of the other, a phenylene group or unsubstituted or substituted naphthylene
 EMI5.4
 by one or more C1-C4 alkyl groups, R14 is hydrogen or a C1-C alkyl group.,
 EMI5.5
 R1S is a hydroxyl group, -o '- MJ group / 4 C1-Cl alkoxy.

   or naked, 5
 EMI5.6
 R16 and R17 are each, independently of the other, hydrogen, CF3 'a C1-C12 alkyl group or a phenyl group, or R16 and R17, with the carbon atom to which they are attached, form a ring of cycloalkylidene to Cc-Co

  <Desc / Clms Page number 6>

 which is unsubstituted or substituted 1 to 3 times by a C1-C4 alkyl group 'R18 and R19 are each, independently of the other, hydrogen, a C1-C4 alkyl group or a phenyl group,
R20 is hydrogen or a C1-C4 alkyl group, R21 is hydrogen or a phenyl group unsubstituted or substituted by one or more C1-C4 alkyl groups; C1-C25 alkyl, C2-C25 alkyl interrupted by
 EMI6.1
 oxygen, sulfur or N-R14;

   C7-C9 phenylalkyl unsubstituted or substituted 1 to 3 times on the phenyl moiety with a C1-C4 alkyl group; C7-C25 phenylalkyl which is unsubstituted or substituted 1 to 3 times on the phenyl moiety with a C1-C4 alkyl group and interrupted
 EMI6.2
 with oxygen, sulfur or N-R .., or radicals. 11 R20 and R21, with the carbon atoms to which they are attached, form a Ce-C cycloalkylene ring. which is unsubstituted or substituted 1 to 3 times by a C1-C4 alkyl group,
R22 is hydrogen or C1-C4 'alkyl
R23 is hydrogen or a C1-C25 alkanoyl group,
 EMI6.3
 C-CE alkenoyl, C-CE alkanoyl interrupted by oxygen, sulfur or N-R ..; C1-C2 alkanoyl substituted with a di (C1-C6 alkyl) phosphonate group;

   Cg-Cq cycloalkylcarbonyl, thénoyie, furoyie, unsubstituted benzoyl or benzoyl substituted by one or more C1-C12 alkyl groups,
 EMI6.4
 

  <Desc / Clms Page number 7>

 
R24 and R25 are each, independently of the other, hydrogen or a C1-C4 alkyl group g,
R26 is hydrogen or a C1-C8 alkyl group,
R27 is a direct bond or a C1-C1 alkylene group, C2-C18 alkylene interrupted by oxygen,
 EMI7.1
 sulfur or N-R14;

   C-C alkenylene <g, C1-alkylidene CC and C, -C cycloalkylene, C-Co'phenylalkylidene in &num; - &num; 0, cycloalkylene in Ce-Co, bicycloalkylene in Cy-Cg, unsubstituted phenylene or phenylene substituted by one or several alkyl groups in
 EMI7.2
 Ci- -C4'Ou, f '-L! R28 is a hydroxyl group, r is a Ci-Ci alkoxy group. ou-nu zu 0 0 R29 is oxygen, -NH- or N-C-NH-F \ o 29 or / N-C-NH-Rm
 EMI7.3
 R30 is a C1-C18 alkyl or phenyl group, R31 is hydrogen or a C1-C18 alkyl group, M is a metal cation of valence r, X is a direct bond, oxygen, sulfur
 EMI7.4
 or-NR-, n is 1 or 2, p is 0.1 or 2, q is 1.2, 3.4, 5 or 6, r is 1.2 or 3, and s is 0.1 or 2.



   A naphthyl, phenanthryl, anthryl, 5.6, 7.8- tetrahydro-2-naphthyl, 5.6, 7, 8-tetrahydro-1-naphthyl, thienyl, benzo [b] thienyl, naphtho [2, 3- b] thienyl, thianthrényle, dibenzofuryle, chroményle, xanthenyle, phenoxathiinyle, pyrrolyle, imidazolyle, pyrazolyle, pyrazinyle, pyrimidinyle, pyridazinyle, indolizinyle, iso-indolyle, indolyle, indazolyle, purazyle, quinininyl, quinolinyl quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, P-carbolinyl, phenanthridinyl, acridinyl, perididinyl,

  <Desc / Clms Page number 8>

 phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, biphenylyl, terphenylyl,

   fluorenyl or phenoxazinyl unsubstituted or substituted by one or more C alkyl groups <-C <, C1-C4 alkoxy, C.sub.1 alkylthio, hydroxyl, halogen, amino, CC alkylamino, phenylamino or di (C1-C4 alkyl) amino is, for example, a 1-naphthyl group, 2- naphthyl, 1-phenylamino-4-naphthyl, 1-methylnaphthyl, 2-methylnaphthyl, 1-methoxy- 2-naphthyl, 2-methoxy-1-naphthyl, 1-dimethylamino-2-naphthyl, 1,2-dimethyl-4- naphthyl, 1,2-dimethyl-6-naphthyl, 1,2-di-
 EMI8.1
 methyl-7-naphthyl, 1, 3-dimethyl-6-naphthyl, 1, 4-dimethyl- 6-naphthyl, 1, 5-dimethyl-2-naphthyl, 1, 6-dimethyl-2-naphthyl, 1-hydroxy- 2-naphthyl, 2-hydroxy-1-naphthyl, 1, 4-dihydroxy- 2-naphthyl, 7-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl,

     3-benzo [b] thienyl, 5-benzo [b] thienyl, 2-benzo- [b] thienyl, 4-dibenzofuryle, 4,7-dibenzofuryle, 4-methyl- 7-dibenzofuryle, 2-xanthenyl, 8-methyl -2-xanthenyl, 3-xanthenyl, 2-phenoxathiinyl, 2,7-phenoxathiinyl,
 EMI8.2
 2-pyrrolyle, 3-pyrrolyle, 5-methyl-3-pyrrolyle, 2-imidazolyle, 4-imidazolyle, 5-imidazolyle, 2-methyl-4-imidazolyle, 2-ethyl-4-imidazolyle, 2-ethyl-5- imidazolyle, 3-pyrazolyle, 1-methyl-3-pyrazolyle, 1-propyl-4-pyrazolyle, 2-pyrazinyle, 5, 6-dimethyl-2-pyrazinyle, 2-indolizinyle, 2-methyl-3-isoindolyle, 2- methyl-1-iso-indolyl, 1-methyl-2-indolyl, 1-methyl-3-indolyl, 1, 5-dimethyl-2-indolyl, 1-methyl- 3-indazolyl, 2, 7-dimethyl-8- purinyl, 2-methoxy-7-methyl-8-purinyl, 2-quinolizinyl, 3-isoquinolyle, 6-isoquinolyle, 7-isoquinolyle, isoquinolyle, 3-methoxy-6-isoquinolyle,

   
 EMI8.3
 2-quinolyl, 6-quinolyl, 7-quinolyl, 2-methoxy-3-quinolyl, 2-methoxy-6-quinolyl, 6-phthalazinyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl, 1, 4-dimethoxy- 6-phthalazinyl, 1,8-naphthyridine-2-yl, 2-quinoxalinyl, 6-quinoxalinyl, 2,3-dimethyl-6-quinoxalinyl, 2,3-dimethoxy-6-quinoxalinyl, 2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino-6-quinazo-
 EMI8.4
 linyl, 3-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 3-methoxy-7-cinnolinyl, 2-pteridinyl, 6-pteridinyl, 7-pteridinyl, 6, 7-dimethoxy-2-pteridinyl, 2-carbazolyl,

  <Desc / Clms Page number 9>

 3-carbazolyl, 9-methyl-2-carbazolyl, 9-methyl-3-carbazolyl, ss-carboline-3-yle, 1-methyl-ss-carboline-3-yle, 1-methyl-ss-carboline-6- yl, 3-phenanthridinyl, 2-acridinyl, 3-acridinyl, 2-perididinyl,

     1-methyl-5-perididinyl, 5-phenanthrolinyl, 6-phenanthrolinyl, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazinyl, 3-phenothiazinyl, 10-methyl- 3- phenothiazinyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 4-methyl-3-furazanyl, 2-phenoxazinyl or 10-methyl-2-phenoxazinyl.



   Particular preference is given to a naphthyl, phenanthryl, anthryl, 5,6, 7,8-tetrahydro-2-naphthyl, 5,6, 7, 8-tetrahydro-1-naphthyl, Lhiényle, benzo- [b] thienyle , naphtho [2, 3-b] thienyl, thianthenyl, dibenzofuryl, chromenyl, xanthenyl, phenoxathiinyl, pyrrolyl, iso-indolyl, indolyl, phenothiazinyl, biphenylyl, terphenylyl, fluorenyl or phenoxazinyl unsubstituted or substituted by C1 or more than one substituted or substituted by C1 or -C4 'alkoxy in C.-C., alkylthio in Cl-C4, hydroxyl, phenylamino
 EMI9.1
 or di (C1-C4 alkyl) amino, for example 1-naphthyl, 2-naphthyl, 1-phenylamino-4-naphthyl, 1-methylnaphthyl, 2-methylnaphthyl, 1-methoxy-2-naphthyl, 2-methoxy-1 -naphthyl, 1-dimethylamino-2-naphthyl, 1,

   2-dimethyl-4-naphthyl, 1, 2-dimethyl-6-naphthyl, 1, 2-dimethyl-7-naphthyl, 1, 3-dimethyl-6-naphthyl, 1, 4-dimethyl-6-naphthyl, 1, 5-dimethyl- 2-naphthyl, 1, 6-dimethyl-2-naphthyl, 1-hydroxy-2-naphthyl, 2-hydroxy-1-naphthyl, 1, 4-dihydroxy-2-naphthyl, 7-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl, 3-benzo [b] thienyl, 5-benzo [b] thienyl, 2-benzo [b] thienyl, 4-dibenzofuryle, 4,7-dibenzofuryle, 4-methyl- 7-dibenzofuryl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl, 2-pyrrolyl, 3-pyrrolyl, 2-phenothiazinyl, 3-phenothiazinyl or 10-methyl-3-phenothiazinyl.



   A halogen (halogen) is, for example, chlorine, bromine or iodine. Chlorine is preferred.



   An alkanoyl group having up to 25 carbon atoms is a branched or unbranched radical, for example

  <Desc / Clms Page number 10>

 formyl, acetyl, propionyl, butyryl, pentanole, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, pentadecanoyl, hexadecanoyle, heptadecanoyle, octadecanoyle



  Preference is given to an alkanoyl group having 2 to 18, in particular 2 to 12, for example 2 to 6, carbon atoms.



  The acetyl group is particularly preferred.



   A C2-C25 alkanoyl group substituted by a
 EMI10.1
 di (C1-C6 alkyl) phosphonate group is, for example, (CHCHO) POCHCO-, (CHO) POCHCO-, (CHCHCHCHO) POCHCO-, (CHCHO) POCHCHCO-, (CHO) POCHCHCO-, (CHCHCHCHO) POCHCHCO -, (CHCHO) PO (CH) CO-, (CHCHO) PO (CH) gCO- or (CHCHO) PO (CH) CO-.



   An alkanoyloxy group having up to 25 carbon atoms is a branched or unbranched radical, for example formyloxy, acetoxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy, decanoyloxy, undécanoyioxy, dodecanoyloxy, tridecanoy
 EMI10.2
 tetradecanoyloxy, pentadecanoyloxy, hexadecanoyloxy, heptadecanoyloxy, octadecanoyloxy, eicosanoyloxy or docosanoyloxy. Preference is given to an alkanoyioxy group having 2 to 18, in particular 2 to 12, for example 2 to 6, carbon atoms. The acetoxy group is particularly preferred.



   An alkenoyl group having 3 to 25 carbon atoms is a branched or unbranched radical, for example propenoyl, 2-butenoyl, 3-butenoyl, isobutenyl, n-2, 4-pentadienoyl, 3-methyl-2-butenoyl, n- 2-octenoyl,
 EMI10.3
 n-2-dodecenoyl, isododecenoyl, oleoyl, n-2-octadecenoyl or n-4-octadecenoyl. Preference is given to an alkenoyl group having 3 to 18, in particular 3 to 12, for example 3 to 6, in particular 3 or 4 carbon atoms.



   A C3-C25 alkenoyl group interrupted by
 EMI10.4
 oxygen, sulfur or N-R ... is, for example, CH30CH2CH2- 11, 14 3 2 2- CH = CHCO- or CH .. OCH., CHOCH = CHCO-.



   An alkenoyloxy group having 3 to 25 carbon atoms is a branched or unbranched radical, for example

  <Desc / Clms Page number 11>

 propenoyloxy, 2-butenoyloxy, 3-butenoyloxy, isobutenyloyloxy, n-2,4-pentadienoyloxy, 3-methyl-2-butenoyloxy, n-2-octenoyloxy, n-2-dodecenoyloxy, isododecenoyloxy, oleoyloxy, n-2- octadecenoyloxy or n-4-octadecenoyloxy. Preference is given to an alkenoyloxy group having 3 to 18, in particular 3 to 12, for example 3 to 6, in particular 3 or 4 carbon atoms.



   A C3-C25 alkenoyloxy group interrupted by
 EMI11.1
 oxygen, sulfur or N-R. is, for example,. 11 CHOCHCHCH = CHCOO- or CHOCHCHOCH = CHCOO-.



  A C-Ce alkanoyl group interrupted by oxygen, sulfur or N-R. is, for example, CH3-0-CH2CO-, CH3-S-CH2CO-, CH3-NH-CH2CO-, CH3-N (CH3) -CH2CO-, CH3-0-CH2CH2-0-CH2CO-, CH3- ( O-CH2CH2-) 20-CH2CO-, CH3- (0-CH2CH2-) 30-CH2CO- or CH3- (0-CH2CH2-) 40-CH2CO-.



  A C3-C25 alkanoyloxy group interrupted by oxygen, sulfur or, NR is, for example, CH3-0- 14 3-0CHCOO-, CH-S-CHCOO-, CH-NH-CHCOO-, CH- N (CH) -CHCOO-, CH3-0-CH2CH2-0-CH2COO-, CH3- (O-CH2CH2-) 20-CH2COO-, CH3- (0-CH2CH2-) 30-CH2COO- or CH3- (0- CH2CH2-) 40-CH2COO-.



   A C6-Cn cycloalkylcarbonyl group is, for example, a cyclohexylcarbonyl, cycloheptylcarbonyl or cyclooctylcarbonyl group. The cyclohexylcarbonyl group is preferred.



   A Cc-C6 cycloalkylcarbonyloxy group is, for example, a cyclohexylcarbonyloxy, cycloheptylcarbonyloxy or cyclooctylcarbonyloxy group. The cyclohexylcarbonyloxy group is preferred.



   A benzoyl group substituted by one or more
 EMI11.2
 C-C alkyl groups and C-alkyl groups <-C, which preferably bears 1 to 3, in particular 1 or 2 alkyl groups, is for example an o-, m or p-methylbenzoyl, 2,3-dimethylbenzoyl, 2,4-dimethylbenzoyl, 2,5-dimethylbenzoyl group , 2,6-dimethylbenzoyl, 3,4-dimethylbenzoyl, 3,5-dimethylbenzoyl, 2-methyl- 6-ethylbenzoyl, 4-tert-butylbenzoyl, 2-ethylbenzoyl, 2,4, 6-trimethylbenzoyl, 2, 6-dimethyl -4-tert-butylbenzoyle or 3,5-di-tert-butylbenzoyle. Preferred substituents are

  <Desc / Clms Page number 12>

 C1-C4 alkyl groups, especially C1-C4 alkyl.



   A benzoyloxy group substituted by one or more
 EMI12.1
 C alkyl groups C alkyl groups <-C <, which preferably has 1 to 3, in particular 1 or 2 alkyl groups, is for example an o-, m- or p-methylbenzoyloxy, 2,3-dimethylbenzoyloxy, 2,4-dimethylbenzoyloxy, 2, 5-dimethylbenzoyloxy group, 2, 6-dimethyl-benzoyloxy, 3, 4-dimethylbenzoyloxy, 3,5-dimethylbenzoyloxy, 2-methyl-6-ethylbenzoyloxy, 4-tert-butylbenzoyloxy, 2-ethylbenzoyloxy, 2,4, 6-trimethylbenzoyloxy, 2, 6- dimethyl-4-tert-butylbenzoyloxy or 3,5-di-tert-butylbenzoyloxy. Preferred substituents are C1-C8 alkyl groups, especially C1-C4 alkyl.



   An alkyl group having up to 25 carbon atoms is a branched or unbranched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl , isopentyl, 1-methylpentyl, 1, 3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyle, 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, eicosyle or docosyle.

   One of the preferred meanings for R2 and R4 is, for example, a C1-C6 alkyl group. A particularly preferred meaning for R4 is a C1-C4 alkyl group.



   An alkenyl group of 3 to 25 carbon atoms is a branched or unbranched radical, for example propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2, 4-pentadienyl, 3-methyl-2-butenyl, n- 2-octenyl, n-2-dodecenyl, isododecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preference is given to an alkenyl group having 3 to 18, in particular 3 to 12, for example 3 to 6, in particular 3 or 4 carbon atoms.



   An alkenyloxy group having 3 to 25 carbon atoms is a branched or unbranched radical, for example

  <Desc / Clms Page number 13>

 propenyloxy, 2-butenyloxy, 3-butenyloxy, isobutenyloxy, n-2,4-pentadienyloxy, 3-methyl-2-butenyloxy, n-2-octenyloxy, n-2-dodecenyloxy, isododecenyloxy, oleyloxy, n-2-octa- decenyloxy or n-4-octadecenyloxy. Preference is given to an alkenyloxy group having 3 to 18, in particular 3 to 12, for example 3 to 6, in particular 3 or 4 carbon atoms.



   An alkynyl group having 3 to 25 carbon atoms is a branched or unbranched radical, for example propynyl (-CH-CCH), 2-butynyl, 3-butynyl, n-2-octynyl, or n-2-dodecynyl. Preference is given to an alkynyl group having 3 to 18, in particular 3 to 12, for example 3 to 6, in particular 3 or 4 carbon atoms.



   An alkynyloxy group having 3 to 25 carbon atoms is a branched or unbranched radical, for example propynyloxy (-OCH2-C = CH), 2-butynyloxy, 3-butynyloxy, n-2-octynyloxy or n-2-dodecynyloxy. Preference is given to an alkynyloxy group having 3 to 18, in particular 3 to 12, for example 3 to 6, in particular 3 or 4 carbon atoms.



   A C-Ce alkyl group interrupted by
 EMI13.1
 oxygen, sulfur or, N-R is, for example, CH3-0-CH2- '. 11 14 3-0-CH2-1 CH3-S-CH2-'CH3-NH-CH2-'CH3-N (CH3) -CH2- 'CH3-0-CH2CH2-0-CH2-' CH3- (O-CH2CH2 -) 20-CH2- 'CH3- (O-CH2CH2-) 30-CH2- or CH3- (O-CH2CH2-) 40-CH2-'
A Cy-Cq phenylalkyl group is, for example, a benzyl, a-methylbenzyl, a, a-dimethylbenzyl or 2-phenylethyl group. Benzyl and α, α-dimthylbenzyl are preferred.



   A Cy-Cn phenylalkyl group which is unsubstituted or substituted 1 to 3 times on the phenyl moiety by a C1-C4 alkyl group is, for example a benzyl, a-methylbenzyl, a, a-dimethylbenzyl, 2-phenyl group. - ethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2, 6-dimethylbenzyl or 4-tert-butylbenzyl. The benzyl group is preferred.



   A C7-C25 phenylalkyl group which is unsubstituted or substituted 1 to 3 times on the phenyl moiety

  <Desc / Clms Page number 14>

 by a C1-C4 alkyl group and which is interrupted by oxygen, sulfur or N-R. is a branched or unbranched radical, for example phenoxymethyl, 2-methylphenoxymethyl, 3-methylphenoxymethyl, 4-methylphenoxymethyl, 2, 4-dimethyl-phenoxymethyl, 2, 3-dimethylphenoxymethyl, phenylthiomethyl, N-methyl-N-phenylmethyl, ethyl-N-phenylmethyl,
 EMI14.1
 4-tert-butylphenoxymethyl, 4-tert-butylphenoxyethoxymethyl, 2, 4-di-tert-butylphenoxymethyl, 2, 4-di-tert-butylphenoxy-ethoxymethyl, phenoxyethoxyethoxyethoxymethyl, benzyloxymethyl,

   benzyloxyethoxymethyl, N-benzyl-N-ethylmethyl or N-benzyl-N-isopropylmethyl.



   A C 7 -C 9 phenylalkoxy group is, for example, a benzyloxy, a-methylbenzyloxy, a, a-dimethylbenzyloxy or 2-phenylethoxy group. The benzyloxy group is preferred.



   A phenyl group substituted by one or more
 EMI14.2
 C-C alkyl groups C-alkyl groups <-C., Which preferably contains 1 to 3, in particular 1 or 2 alkyl groups, is for example an o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5 group -dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl or 2, 6-diethylphenyl.



   A phenoxy group substituted by one or more
 EMI14.3
 C-C alkyl groups e C-alkyl groups <-C., Which preferably contains 1 to 3, in particular 1 or 2 alkyl groups, is for example an o-, m- or p-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2, 5 group -dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2-methyl-6-ethylphenoxy, 4-tert-butylphenoxy, 2-ethylphenoxy or 2, 6-diethylphenoxy.
 EMI14.4
 



  ,-VS. unsubstituted 'A C 1 -C 6 cycloalkyl group which is unsubstituted or substituted by one or more C 1 -C 4 alkyl groups is, for example, a cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl group,
 EMI14.5
 dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, cycloheptyl or cyclooctyl. Cyclohexyl and tert-butylcyclohexyl groups are preferred.



   A C5-C8 cycloalkoxy group which is unsubstituted or substituted by one or more C1-C4 alkyl groups is,

  <Desc / Clms Page number 15>

 for example, a cyclopentoxy, methylcyclopentoxy, dimethylcyclopentoxy, cyclohexoxy, methylcyclohexoxy group,
 EMI15.1
 dimethylcyclohexoxy, trimethylcyclohexoxy, tert-butylcyclohexoxy, cycloheptoxy or cyclooctoxy. Cyclohexoxy and tert-butylcyclohexoxy groups are preferred.



   An alkoxy group having up to 25 carbon atoms is a branched or unbranched radical, for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. Preference is given to an alkoxy group having 1 to 12, in particular 1 to 8, for example 1 to 6 carbon atoms.



   A C2-C25 alkoxy group interrupted by oxygen, sulfur or N-R14 is, for example,
 EMI15.2
 CH3-0-CH2CH20-, CH3-S-CH2CH20-, CH3-NH-CH2CH20-, CH3-N (CH3) CH2CH20-, CH3-0-CH2CH2-0-CH2CH20-, CH3- (O-CH2CH2-) 20 -CH2CH20-, CH3- (O-CH2CH2-) 30-CH2CH20- or CH3- (0-CH2CH2-) 40-CH2CH20-.



   An alkylthio group having up to 25 carbon atoms is a branched or unbranched radical, for example methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, pentylthio, isopentylthio, hexylthio, heptylthio, octylthio, decylthio, tetradecylthio, or octadecylthio. Preference is given to an alkylthio group having 1 to 12, in particular 1 to 8, for example 1 to 6 carbon atoms.



   An alkylamino group having up to 4 carbon atoms is a branched or unbranched radical, for example methylamino, ethylamino, propylamino, isopropylamino, n-butylamino, isobutylamino or tert-butylamino.
 EMI15.3
 



  A di (C1-C4 alkyl) amino group is also 1-C4 e a group in which each of the two alkyl radicals is, independently of the other, branched or unbranched, for example dimethylamino, methylethylamino, diethylamino, methyl-n -propylamino, methylisopropylamino, methyl-n-butylamino, methylisobutylamino, ethylisopropylamino, ethyln-butylamino, ethylisobutylamino, ethyl-tert-butylamino, diethylamino, diisopropylamino, isopropyl-n-butylamino, isopropylisino butino

  <Desc / Clms Page number 16>

 
 EMI16.1
 



  An alkanoylamino group having up to 25 carbon atoms is a branched or unbranched radical, for example formylamino, acetylamino, propionylamino, butyrylamino, pentanoylamino, hexanoylamino, heptanoylamino, octanoylamino, nonanoylamino, decanoylamino, undécanoylamino, dececanoylamino, dodecanoylamino, , hexadecanoylamino, heptadecanoylamino, octadecanoylamino, eicosanoylamino or docosanoylamino.



  Preference is given to an alkanoylamino group having 2 to 18, in particular 2 to 12, for example 2 to 6 carbon atoms.



  A C1-C18 alkylene group is a branched or unbranched radical, for example methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene or octadecamethylene. Preference is given to a C-C alkylene group. <-C <, in particular C1-C6 alkylene. A C6-C12 cycloalkylene ring substituted by one or more C1-C4 alkyl groups, which preferably contains 1 to 3, in particular 1 or 2 branched or unbranched alkyl groups, is for example a cyclopentylene, methylcyclopentylene, dimethylcyclopentylene, cyclohexylene, methylcyclohexylene, dimethylcyclohexylene, trimethylcyclohexylene, tert-butylcyclohexylene, cycloheptylene, cyclooctylene or cyclodecylene group.

   Cyclohexylene and tert-butylcyclohexylene groups are preferred.



  A C2-C18 alkylene group interrupted by oxygen, sulfur or N-R. is, for example, -CH2-0-CH2- '. 11 14 2-0-CH2-1 - CH2-S-CH2 -, - CH2-NH-CH2 -, - CH2-N (CH3) -CH2 -, - CH2-0-CH2CH2O-CH2 -'- CH2- ( O-CH2CH2-) 20-CH2- '-CH2- (O-CH2CH2-) 30-CH2-' - CH2- (0-CH2CH2-) 40-CH2- or-CH2CH2-S-CH2CH2-.



  A C2-C18 alkenylene group is for example a vinylene, methylvinylene, octenylethylene or dodecenylethylene group. Preference is given to a C2-C8 alkenylene group.



  An alkylidene group having 2 to 20 carbon atoms is, for example, an ethylidene, propylidene group,

  <Desc / Clms Page number 17>

 butylidene, pentylidene, 4-methylpentylidene, heptylidene, nonylidene, tridecylidene, nonadecylidene, 1-methyl-ethylidene, 1-ethylpropylidene or 1-ethylpentylidene.



  Preference is given to a C 1 -C 6 alkylidene group.



   A phenylalkylidene group having 7 to 20 carbon atoms is, for example, a benzylidene, 2-phenylethylidene or 1-phenyl-2-hexylidene group. We give preference
 EMI17.1
 to a phenylalkylidene group at Cy-Cq.



  A C 6 -C 8 cycloalkylene group is a saturated hydrocarbon group having two free valencies and at least one cyclic unit and it is, for example, a cyclopentylene, cyclohexylene, cycloheptylene or cyclooctylene group. The cyclohexylene group is preferred.



   A C7-C8 bicycloalkylene group is, for example, a bicycloheptylene or bicyclooctylene group.



   A phenylene or naphthylene group unsubstituted or substituted by one or more C1-C4 alkyl groups is, for example, a group 1,2-, 1,3-, 1,4-phenylene, 1,2-, 1,3 -, 1,4-, 1,6-, 1,7-, 2, 6- or 2,7-naphthylene. The 1,4-phenylene group is preferred.
 EMI17.2
 



  A C-C6 cycloalkylidene ring substituted by one or more C1-C4 alkyl groups, which preferably contains 1 to 3, in particular 1 or 2 branched or unbranched alkyl groups, is for example a cyclopentylidene, methylcyclopentylidene, dimethylcyclopentylidene group, cyclohexylidene, methylcyclohexylidene, dimethylcyclohexylidene, trimethylcyclohexylidene, tert-butylcyclohexylidene, cycloheptylidene or cyclooctylidene. Cyclohexylidene and tert-butylcyclohexylidene groups are preferred.



   A mono-, di- or trivalent metal cation is preferably an alkali metal, alkaline earth metal or aluminum cation, for example Na, K, Mg, Ca ..-, +++ or Al
Compositions which are of interest include those containing, as component (b), at least one compound of formula I in which, if n is 1, R. is an unsubstituted phenyl group or phenyl which is substituted for the

  <Desc / Clms Page number 18>

 para position through a C1-C18 alkylthio or di (C1-C4 alkyl) amino group; a phenyl group substituted by 1 to 5 alkyl groups having not more than 18 carbon atoms in total in the 1 to 5 alkyl substituents;

   or a naphthyl, biphenylyl, terphenylyl, phenanthryl, anthryl, fluorenyl, carbazolyl, thienyl, pyrrolyl, phenothiazinyl group or 5,6, 7,8-tetrahydronaphthyl unsubstituted or substituted by one or more C 1 -C alkyl groups, alkoxy Cl-C4 'C1-C4 alkylthio, hydroxyl or amino.



   Preferred compositions contain, as component (b), at least one compound of formula I in which, if n is 2,
 EMI18.1
 R1 is -R12-X-R13- 'R12 and R13 are phenylene groups, X is oxygen or-NR <-, and
R31 is a C1-C4 alkyl group.



   Preferred compositions also contain, as component (b), at least one compound of formula I in which, if n is 1, R1 is a naphthyl, phenanthryl, thienyl, dibenzofuryl, carbazolyl or fluorenyl group substituted by one or more alkyl groups C1-C4, C1-C6 alkoxy, C1-C4 alkylthio, hydroxyl, halo, amino, C1-C4 alkylamino or di (C1-C4 alkyl) amino, or a group of formula II
 EMI18.2
   Ry, Rg, Rg, Ro and R11 are each, independently of the others, hydrogen, chlorine, bromine or a hydroxyl group, C1-C8 alkyl, C2-C18 alkyl interrupted by oxygen or sulfur; C1-C18 alkoxy, C2-C18 alkoxy interrupted by oxygen or sulfur;

   C1-C18 alkylthio, C3-C12 alkenyloxy, C3-C12 alkynyloxy 'C7-C9 phenylalkyl, Cy-Cg phenylalkoxy; phenyl unsubstituted or substituted by one or more alkyl groups

  <Desc / Clms Page number 19>

 in C1-C4; phenoxy, cyclohexyl, C 6 -C cycloalkoxy, C 1 -C 4 alkylamino, di (C 1 -C 4 alkyl) amino, alkanoyl
 EMI19.1
 in C.-C, alkanoyie in C-C <interrupted by oxygen or sulfur; C1-C6 alkanoyloxy, C3-C12 alkanoyloxy interrupted by oxygen or sulfur; C1-C12 alkanoylamino C3-C12 alkenoyl C3-C12 alkenoyloxy 1 12, C3-Cl2 alk'noyl, 3-Cl2 'cyclohexylcarbonyl, cyclohexylcarbonyloxy; benzoyl unsubstituted or substituted by one or more alkyl groups
 EMI19.2
 in Cl-C4;

   benzoyloxy unsubstituted or substituted by
 EMI19.3
 R 0 118 It one or more C1-C4'-O-C-C-R alkyl groups or zu 1 R19 21 M19 1 1 - 0-C-C-0-FL, 3, or, in formula II, the radicals H Ruz
 EMI19.4
 R7 and Rg or the radicals R8 and Roll, with the carbon atoms to which they are attached, form a joined benzene nucleus,
 EMI19.5
 R15 is a hydroxyl group, C1-C12 alkoxy or-nose
 EMI19.6
 R. g and R19 are each, independently of the other, hydrogen or a C1-C4 alkyl group,
R20 is hydrogen,
R21 is hydrogen or phenyl, C1-C18 alkyl, C2-C18 alkyl interrupted by oxygen or sulfur;

   C7-C9 phenylalkyl, C7-C18 phenylalkyl which is unsubstituted or substituted 1 to 3 times on the phenyl moiety by a C1-C4 alkyl group and which is interrupted by oxygen or sulfur, or radicals R20 and
 EMI19.7
 21, with the carbon atoms to which they are attached, R es, form a cyclohexylene ring unsubstituted or substituted 1 to 3 times by a C1-C4 alkyl group,
R22 is hydrogen or C1-C4 'alkyl
R23 is hydrogen or a C1-C18 alkanoyl, C3-C18 alkenoyl, C3-Cl2 alkanoyl interrupted by oxygen or sulfur; C2-C12 alkanoyl substituted by

  <Desc / Clms Page number 20>

 a di (C1-C6 alkyl) phosphonate group;

   Cg-Cn cycloalkylcarbonyl, benzoyl,
 EMI20.1
 
 EMI20.2
 R24 and R25 are each, independently of the other, hydrogen or a C1-C12 alkyl group 'R26 is hydrogen or a C1-C4 alkyl group' R27 is a C-alkylene group <-C, 27 l-Cl2 alkenylene, C-Cg alk'nyl ', C-Cg alkylidene, phenylalkylidene in Cy-C, cycloalkylene in Ce-Cg or phenylene,
 EMI20.3
 R28 is a hydroxyl, C1-Cl2 / 4 or -N RM alkoxy group
 EMI20.4
 R29 is oxygen or -NH-, R30 is a C1-Cl alkyl group. or phenyl, and s is 1 or 2.



   Preferred compositions also contain, as component (b), at least one compound of formula I in which, if n is 1, R1 is a phenanthryl, thienyl, dibenzofuryl group; carbazolyl unsubstituted or substituted by one or more C1-C4 alkyl groups; or fluorenyl; or R1 is a group of formula II

  <Desc / Clms Page number 21>

 
 EMI21.1
 
 EMI21.2
 Ry, Rg, Rg, R.

   Q and R11 are each, independently of the others, hydrogen, chlorine or a hydroxyl, C alkyl group <-C <g, C1-Cl alkoxy, C-alkylthio <-C <g, C-C alkenyloxy <, C-C alkynyloxy <, phenyl, benzoyie,
 EMI21.3
 R R, R2Q R21 benzoyloxy ou-O-C-C-O-Rm, 1 1 H R
 EMI21.4
 R20 is hydrogen, R21 is hydrogen or a phenyl or C1-Cl alkyl group, or else the radicals R20 and R21, with the carbon atoms to which they are attached, form an unsubstituted or substituted cyclohexylene ring 1 to 3 times with a C1-C4 alkyl group,
R22 is hydrogen or a C1-C4 alkyl group, and
 EMI21.5
 R23 is hydrogen, a C1-C12 alkanoyl group or a benzoyl group.



   Particularly preferred compositions contain, as component (b), at least one compound of formula I in which, if n is 1,
R7, R8, R9, R10 and R11 are each, independently of the others, hydrogen or a C1-C12 alkyl group C1-C4 alkylthio or phenyl.



   Particularly advantageous compositions contain, as component (b), at least one compound of formula I in which R, R, R. and Re are each, independently of the others, hydrogen, chlorine or an alkyl group in
 EMI21.6
 Ci-Cl., Benzyl, Phenyl, C 1-6 cycloalkyl, Cl-Cl alkoxy, Cl-Cl alkylthio, Cl-Cl alkanoyloxy, C.-C. alkanoylamino o, alkenoyioxy enC-C. n or benzoyioxy;

   or the radicals R2 and R3 or the radicals R3 and R4 or the radicals R4 and Ré, with the carbon atoms to which

  <Desc / Clms Page number 22>

 they are fixed, form a joined benzene nucleus, and R4
 EMI22.1
 can also be- (CH) -CORou- (CHL) OH, or, if R, Rc and R6 are each hydrogen, R4 can also be a group of formula III,
 EMI22.2
 R <c is a hydroxyl group, C1-C12 alkoxy or -N 11, R24 'R24' 'R2s,
R16 and R17 are methyl groups or else, with the carbon atom to which they are attached, they form a cycloalkylidene ring in Ce-Cg which is unsubstituted or substituted 1 to 3 times by a C1-C4 alkyl group,
R24 and R25 are each, independently of the other, hydrogen or a C1-Cl2 alkyl group 'p is 1 or 2, and q is 2,3, 4,5 or 6.



   Particularly advantageous compositions also contain, as component (b), at least one compound of formula I in which at least two of the radicals R, R, R. and Re are hydrogen.



   Especially interesting compositions contain, as component (b), at least one compound of formula I in which the radicals R3 and Rc are hydrogen.



   Especially advantageous compositions contain, as component (b), at least one compound of formula I in which
R2 is a C1-C4 alkyl group,
R3 is hydrogen,
R4 is a C1-C4 alkyl group or, if R6 is hydrogen, R4 can also be a group of formula III, Re is hydrogen, and R. g and R. y, with the carbon atom to which they are attached form a cyclohexylidene cycle.



   The following compounds are examples of compounds with a benzofuran-2-one structure which are particularly suitable as component (b) in the new composition:

  <Desc / Clms Page number 23>

   3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2-one; 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one; 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one]; 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one; 3- (4-acetoxy-
 EMI23.1
 3,5-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one; 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzo-furan-2-one; 5,7-di-tert-butyl-3-phenylbenzofuran-2-one; 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) benzofuran-2-one;

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



   Especially interesting compositions also contain, as component (b), at least one compound corresponding to formula V
 EMI23.2
 in which
R2 is hydrogen or a C1-C6 alkyl group,
R3 is hydrogen,
R4 is hydrogen or a C1-C6 alkyl group; Re is hydrogen,
R7, R8, R9, R10 and R11 are each, independently of the others, hydrogen, a C1-C4 alkyl group or a C1-C4 alkoxy group, provided that at least two of the radicals R7, R8, R9 , R10 and R11 are hydrogen.



   Very particularly preferred compositions contain, as component (b), at least one compound of formula Va or Vb

  <Desc / Clms Page number 24>

 
 EMI24.1
 or a mixture of the two compounds of formulas Va and Vb.



   The compounds with a benzofuran-2-one structure used as component (b) of the new composition are known in the literature and their preparation is described, for example, in the following US patents: No. 4,325,863, 4,388,244, 5 175 312, 5 252 643, 5 216 052, 5 369 159.5 488 117.5 356 966.5 367 008.5 428 162, 5 428 177 and 5 516 920.



   Particularly advantageous compositions contain, as component (c), at least one compound chosen from the class of organic phosphites and phosphonites corresponding to formulas 1 to 7
 EMI24.2
 

  <Desc / Clms Page number 25>

 
 EMI25.1
 in which the indices are whole numbers and is not 2,3 or 4, p is 1 or 2, q is 2 or 3, r is from 4 to 12, y is 1,2 or 3, and z is from 1 to 6, if not 2, A is a C2-C18 alkylene group 'C2-C12 alkylene interrupted by oxygen, sulfur or -NR'4-, a group of formula
 EMI25.2
 
 EMI25.3
 or phenylene;

   if is 3, A is a group of formula "C'H, ..-,
 EMI25.4
 cHîI 2 if not 4, A is-CH-C-CH-, CH2 2
 EMI25.5
 A "is defined as for A'si is not 2, B is a direct bond, -CH -, - CHR '.-, -CR'R.-, sulfur or a Cs-C7 cycloalkylidene group or is a cyclohexylidene group substituted by 1 to 4 C1-C4 alkyl groups in positions 3, 4 and / or 5, if p is 1, D is a methyl group and, if p 'is 2, D'est-CHOCH -, if y is 1, E is a C 1 -C alkyl group, - OR '., or a halogen, if y is 2, E is-OA "-O-, if y' is 3, E is a group of formula R'4C (CH20-) 3 or N (CHCHO-), Q is the radical of an alcohol or phenol at least having a valence of at least z ', this radical being attached by the oxygen atom to the phosphorus atom;

   

  <Desc / Clms Page number 26>

 
 EMI26.1
 R ', R' and R'3 are each, independently of the others, a C 1 -C alkyl group g unsubstituted or 1-cl, unsubstituted 'substituted by a halogen, -COOR'4, -CN or -CONR'4R'4; a C2-C18 alkyl group interrupted by oxygen, sulfur or -NR'4-; a C7-C9 phenylalkyl group; a C 1-6 cycloalkyl, phenyl or naphthyl group; a naphthyl or phenyl group substituted by a halogen, by 1 to 3 alkyl or alkoxy groups having in total 1 to 18 carbon atoms or by a phenyl-C 7 -C 9 alkyl group;

   or a group of formula
 EMI26.2
 where me is an integer from 3 to 6;
R'4 is hydrogen or a C1-C18 alkyl group,
 EMI26.3
 C1-C12 cycloalkyl or Cy-Cq phenylalkyl, R'E and R'6 are each, independently of the other, hydrogen, C1-C6 alkyl. or a C1-C6 cycloalkyl group, if q′s 2, R′7 and R′8 are each, independently of the other, a C1-C4 alkyl group or together form a 2,3-dehydropentamethylene group; and
 EMI26.4
 if q is 3, R'7 and R'o are methyl groups;

   R'14 is hydrogen, a C1-C9 alkyl group or a cyclohexyl group,
R'15 is hydrogen or a methyl group and, if two or more radicals R'14 and R'15 are present, these radicals are identical or different,
X 'and Y' are each a direct bond or oxygen, z is a direct bond, a methylene group, -C (R'16) 2- or sulfur, and
R'16 is a C1-C8 alkyl group.



   Particularly advantageous compositions contain, as component (c), a phosphite or phosphonite of the formula 1,2, 5 or 6 in which

  <Desc / Clms Page number 27>

 is the number 2 and y is the number 1,2 or 3, A is a C2-C18'p-phenylene alkylene group or
 EMI27.1
 p-biphenylene, p-biphenylene, if y is 1, E is a C1-Cl alkyl group, - OR'1 or fluorine, if y is 2, E is a p-biphenylene group, if there is 3, E is N (CH2CH20-) 3,
R'1, R'2 and R'3 are each, independently of the others, a C1-C18 alkyl, C7-C9 phenylalkyl, cyclohexyl, phenyl or phenyl substituted by 1 to 3 alkyl groups having in total 1 to 18 carbon atoms,

  
R'14 is hydrogen or a C1-C9 alkyl group
R'15 is hydrogen or a methyl group, X is a direct bond,
Y is oxygen, Z is a direct bond or -CH (R ') -, and R'16 is a C1-C4 alkyl group.



   Interesting compositions also contain, as component (c), a phosphite or phosphonite of the formula 1,2, 5 or 6 in which is not the number 2 and y is the number 1 or 3,
A is a p-biphenylene group, if y is 1, E is a Cl-Cl alkoxy group. or fluorine, if there is 3, E is N (CH2CH20-) 3 '
 EMI27.2
 R ', R' and R'3 are each, independently of the others, a C1-C6 alkyl group, or a phenyl group substituted by 2 or 3 alkyl groups having in total 2 to 12 carbon atoms,
R'14 is a methyl or tert-butyl group,
 EMI27.3
 R'1S is hydrogen, X is a direct bond,
Is oxygen, and
Z is a direct bond, a methylene group or -CH (CH3) -.

  <Desc / Clms Page number 28>

 



   Particularly preferred compositions contain, as component (c), a phosphite or phosphonite of formula 1,2 or 6.



   Especially preferred compositions contain, as component (c), at least one compound corresponding to formula VII
 EMI28.1
 in which R1 and R2 are each, independently of the other, hydrogen or a C1-C6 alkyl, cyclohexyl or phenyl group, and
R3 and R4 are each, independently of the other, hydrogen or a C1-C4 alkyl group.



   The following compounds are examples of organic phosphites and phosphonites which are particularly suitable as component (c) in the new compositions: triphenyl phosphite, diphenyl and alkyl phosphites, phenyl and dialkyl phosphites, tris- (nonylphenyl) phosphite ), trilauryl phosphite, trioctadecyl phosphite, distearyl and pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite (Irgafos 168, Ciba-Geigy), diisodecyl and pentaerythritol diphosphite, diphosphite bis (2,4-di-tert-butylphenyl) and pentaerythritol (formula D), bis (2,6-di-tertbutyl-4-methylphenyl) and pentaerythritol (formula E) diphosphite, bisisodecyloxy-pentaerythritol diphosphite, diphosphite
 EMI28.2
 from bis (2,

   4-di-tert-butyl-6-methylphenyl) and pentaerythritol, bis (2, 4, 6-tri-tert-butylphenyl) and pentaerythritol diphosphite, tristearyl and sorbitol triphosphite, 4, 4'- tetrakis biphenylenediphosphonite (2,4-di-tert-butylphenyl) (IrgafosPEP-Q, Ciba-Geigy, formula H),

  <Desc / Clms Page number 29>

 6-isooctyloxy-2,4, 8, 10-tetra-tert-butyl-1 2H-dibenzo [d, g] - 1,3, 2-dioxaphosphocine (formula C), 6-fluoro-2,4, 8, 10-tetra-
 EMI29.1
 tert-butyl-12-methyldibenzo [d, g] -1, 3, 2-dioxaphosphocine (formula A), bis (2,4-di-tert-butyl-6-methylphenyl) and methyl phosphite, phosphite bis (2,4-di-tert-butyl-6-methylphenyl) and ethyl (formula G).



   Particular preference is given to the use of the following phosphites and phosphonites: tris phosphite (2,4-di-tert-butylphenyl) (Irgafos168, Ciba-Geigy), tris phosphite (nonylphenyl),
 EMI29.2
 

  <Desc / Clms Page number 30>

 
 EMI30.1
 
 EMI30.2
 Particularly preferred are tris (2,4-di-tert-butylphenyl) phosphite [Irgafos168, Ciba Spezialitâtenchemie AG], bis (2,4-di-tert-butyl-6-methylphenyl) and ethyl phosphite [Irgafos38 , Ciba Spezialitâtenchemie AG, formula (G) and tetrakis (2,4-di-tert-butylphenyl) 44'-biphenylenediphosphonite [IrgafosOPEP-Q, Ciba Spezialitâtenchemie AG, formula (H)].



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



  Compositions which are of interest include those containing, as component (d), at least one compound corresponding to formula VI
 EMI30.3
 in which
 EMI30.4
 R1 is a C-C alkyl group n is 1, 2, 3 or 4,

  <Desc / Clms Page number 31>

 
 EMI31.1
 0 0 X is a methylene group, -CH-CH-C-Y-or o - (D-CHI-CHr-,
 EMI31.2
 Y is oxygen or-NH-; and if n is 1,
 EMI31.3
 0 there X is -CH2CH2C-Y-, where Y is fixed to R2, and
 EMI31.4
 R2 is a C1-C25 alkyl group; and if n is 2,
 EMI31.5
 0 There where y is fixed to R2 'X is-CH-CH-C-Y-y where Y is fixed to R, and
 EMI31.6
 R2 is a C-C alkylene group. , C4-C12 alkylene interrupted by oxygen or sulfur; or if Y is-NH-, R can also be a direct bond;

   and, if n is 3,
 EMI31.7
 0 il X is a methylene group or -CH2C-O-CH2CH,
 EMI31.8
 where the ethylene group is attached to R2, and
 EMI31.9
 
 EMI31.10
 if n is 4,
 EMI31.11
 0 il x est-CH-CH.-C-Y-, where Y is fixed to R2, and
 EMI31.12
 R2 is a C4-C10 alkanetetrayl group.



  An alkyl group having up to 25 carbon atoms is a branched or unbranched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl , isopentyl, 1-methyl-pentyl, 1, 3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1, 1, 3, 3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl , 2-ethylhexyl,

  <Desc / Clms Page number 32>

 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyle, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyle or docosyle.



  A preferred meaning for R1 is a methyl and tert-butyl group. A particularly preferred meaning for R2 is a C1-C20 alkyl group, in particular C1-C8 alkyl, for example C4-C18 alkyl. An especially preferred meaning for R2 is a Cg-Cg alkyl group,
 EMI32.1
 especially C-C alkyl <o, for example C1 alkyl.



  A C2-C12 alkylene group is a branched or unbranched radical, for example ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene or dodecamethylene. A preferred meaning for R2 is, for example, a group
 EMI32.2
 C-alkylene C-C alkylene <, especially C2-C8 alkylene. A particularly preferred meaning for R2 is, for example, a C4-C8 alkylene group, in particular C4-C6 alkylene, for example hexamethylene.



   A C4-C12 alkylene group interrupted by
 EMI32.3
 oxygen or sulfur can be discontinued one or more
 EMI32.4
 times and it is, for example, -CH2-0-CH2CH2-O-CH2-, -CH2- (0-CH 2CH2-) 20-CH2-1-CH2- (0-CH2CH 2-) 30- CH2-1 - CH2- (O-CH2CH2-) 40-CH2- '-CH2CH2-0-CH2CH2-0-CH2CH2- or - CH2CH2-S-CH2CH2-. A preferred meaning for R2 is, for example, a C4-C10 alkylene group interrupted by oxygen or sulfur, in particular a C4-C8 alkylene group interrupted by oxygen or sulfur, for example an alkylene radical in C4-C6 interrupted by oxygen or sulfur. A particularly preferred value for R2 is -CH2CH2-O-CH2CH2-O-CH2CH2-or-CH2CH2-S-CH2CH2-.
 EMI32.5
 



  An alkanetetrayl group having 4 to 10 carbon atoms is, for example,
 EMI32.6
 CHi- - CH-C-CHg- (pentaerythrityl), um- 2

  <Desc / Clms Page number 33>

 
 EMI33.1
 
The pentaerythrityl group is preferred.



   Component (d) can also include mixtures of different hindered phenols of formula VI.



   Interesting compositions include those containing, as component (d), at least one compound of formula VI in which, if n is 1, R2 is a C1-C20 alkyl group.



   Preferred compositions contain, as component (d), at least one compound of formula VI in which if n is 2,
R2 is a C2-C8 alkylene, C4-C8 alkylene group interrupted by oxygen or sulfur; or, if Y is - NH-, R can also be a direct bond; and if n is 4,
R2 is a C 1-6 alkanetetrayl radical.



   Preferred compositions also contain, as component (d), at least one compound of formula VI in which R1 is a methyl or tert-butyl group, n is 1, 2 or 4,
 EMI33.2
 0 il X est-CH, -CH, -C-Y-,
 EMI33.3
 Y is oxygen or-NH-; and if n is 1,
R2 is a C14-C18 alkyl group; and if n is 2,
R2 is a C4-C6 alkylene group or a C4-C6 alkylene group interrupted by oxygen;

   and if n is 4,
R2 is a C4-C6 alkanetetrayl radical "

  <Desc / Clms Page number 34>

 
Interesting compositions also contain, as component (d), at least one compound of formula VI which is a compound of one of the formulas VIa to VIh
 EMI34.1
 

  <Desc / Clms Page number 35>

 
 EMI35.1
 

  <Desc / Clms Page number 36>

 
 EMI36.1
 Irganox1098, Irganox1076, Irganox1010, Irganox 245, Irganox259, IrganoxiI3114, Irganox1035 and Irganox3125 are protected trademarks of Ciba Spezialitâtenchemie AG.



   Preferred compositions contain, as component (d), at least one compound of formula VI which is a compound of formula VIa, VIb, Life or VId, in particular a compound of formula VIa, VIb or Life.



   Component (d) of the new composition, and the compounds of formula VI, are known and, in some cases, can be obtained commercially. Possible preparation methods for the compounds of formula VI can be found, for example, in U.S. Patents NO 3,330,859 and 3,960,928.



   Compositions which are of interest include those in which component (e) contains at least one group of formula XII or XIII
 EMI36.2
 
 EMI36.3
 in which G is hydrogen or a methyl group, and G1 and G2 are each hydrogen or a methyl group, or are together oxygen.



  Particularly advantageous compositions are those which contain, as component (e), at least one compound of the class of hindered amines belonging to the family of the compounds described in (a ') to (g') which comprise at least one group of formula XII or XIII.



  (a ') Compounds of formula XIIa
 EMI36.4
 

  <Desc / Clms Page number 37>

 where n is a number from 1 to 4,
G and G1 are each, independently of the other, hydrogen or a methyl group,
G11 is hydrogen, 0 ', a hydroxyl group, NO,
 EMI37.1
 - CHCN, C1-C6 alkyl, C-C8 alkenyl, C-Co alkynyl, Cy-C aralkyl, Ci-Cl alkoxy, Ce-Cg cycloalkoxy, phenylalkoxy in Cy-Cg, C1 alkanoyl -C., C-C alkenoyl, C1-C18 alkanoyloxy, benzyloxy, glycidyl or a group -CH2CH (OH) -Z, G11 preferably being hydrogen or a C1-C4 alkyl group, allyl, benzyl, acetyl or acroyl, z is hydrogen, a methyl group or a phenyl group, and, if n is 1,
G12 is hydrogen,

   a C1-C18 alkyl group which is uninterrupted or interrupted by one or more oxygen atoms, a cyanoethyl, benzyl or glycidyl group, a monovalent radical of a phosphorus acid, a carbamic acid or a carboxylic acid aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic, or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15 carbon atoms, an a, ss unsaturated carboxylic acid having 3 to 5 carbon atoms or an aromatic carboxylic acid having 7 to 15 carbon atoms, the carboxylic acid can in each case be substituted in the aliphatic, cycloaliphatic or aromatic portion
 EMI37.2
 by 1 to 3 COOZ groups, where Z.

   is hydrogen or a C1-C20 alkyl group, C3-C12 alkenyl, C1-cycloalkyl, C3-Cl2 alkynyl, Ce-Cy, phenyl or benzyl, and C, -C e if n is 2,
G12 is a C2-C12 alkylene, a C-alkenylene group <, xylylene, a divalent radical of a phosphorus acid, a carbamic acid or an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, or

  <Desc / Clms Page number 38>

 a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid having 2 to 36 carbon atoms, of a cycloaliphatic or aromatic dicarboxylic acid having 8 to 14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8 to 14 carbon atoms, the dicarboxylic acid can in each case be substituted in the aliphatic portion,

   cycloaliphatic or aromatic by 1 or 2 COOZ groups, and if n is 3,
G12 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, which may be substituted in the aliphatic, cycloaliphatic or aromatic portion by -COOZ12, of an aromatic tricarbamic acid or of a phosphorus acid, or is a silylated radical trivalent, and if n is 4,
G12 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.



   The carboxylic acid radicals indicated include, in each case, the radicals of formula (-CO) nR where n is as defined above and the meaning of R is apparent from the definition given.



   Any C1-C12 alkyl substituent can be, for example, a methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl group. , n-decyl, n-undecyl or n-dodecyl.



   If G11 or G12 is a C1-C1 alkyl group, it may be, for example, one of the groups indicated above and also, for example, an n-tridecyl, n-tetradecyl, n- hexadecyl or n-octadecyl.



   If G11 is a C 1 -C alkenyl group, it may be, for example, a 1-propenyl, allyl, methallyl, 2butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tertbutyl-2-butenyl group.



   If G11 is a C-C6 alkynyl group, it is preferably the propargyl group.

  <Desc / Clms Page number 39>

 



   If G11 is a Cy-C aralkyl group, it is in particular a phenethyl group and in particular benzyl.



   If G11 is a C1-C8 alkanoyl group, it is for example a formyl, propionyl, butyryl, octanoyl group, but preferably acetyl, and if G11 is an alkenoyl group
 EMI39.1
 in C-Ce, it is notably the acrylic group.



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



   If G12 is a monovalent silyl radical, it is for example a group of formula- (C.H) -Si (Z ') 2Z "where j is
 EMI39.2
 an integer from 2 to 5 and Z'and Z "are each, independently of the other, C1-C4 alkyl or C1-C4 alkoxy"
If G12 is a divalent radical of a dicarboxylic acid, it is for example a radical of malonic, succinic, glutaric, adipic, suberic, sebacic, maleic, itaconic, phthalic, dibutylmalonic, dibenzylmalonic, butyl (3, 5- di-tert-butyl-4-hydroxybenzyl) malonic or bicycloheptenedicarboxylic.



   If G. is a trivalent radical of a tricarboxylic acid, it is for example a radical of trimellic, citric or nitrilotriacetic acid.



   If G12 is a tetravalent radical of a tetracarboxylic acid, it is for example the tetravalent radical of butane-1,2,3,4-tetracarboxylic acid or of pyromellic acid.



   If G12 is a divalent radical of a dicarbamic acid, it is for example a radical of hexamethylenedicarbamic acid or 2,4-tolylenedicarbamic acid.



   Preference is given to the compounds of formula XIIa in which G is hydrogen, G11 is hydrogen or a methyl group, n is 2 and G12 is the diacyl radical of an aliphatic dicarboxylic acid having 4 to 12 carbon atoms .

  <Desc / Clms Page number 40>

 



   Examples of polyalkylpiperidines in this category are the following compounds:
1) 4-hydroxy-2,2,6,6-tetramethylpiperidine
2) 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
3) 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
4) 1- (4-tert-butyl-2-butenyl) -4-hydroxy-2, 2,6, 6-tetramethylpiperidine
5) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine
6) 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine
7) 4-methacroyloxy-1,2, 2,6, 6-pentamethylpiperidine
 EMI40.1
 8) ss- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate of 1, 2, 2, 6, 6-pentamethylpiperidine-4-yl 9) bis maleate (2-benzyl-2, 2, 6, 6-tetramethylpiperidine-4-yle) 10) bis succinate (2, 2, 6, 6-tetramethylpiperidine-4-yle) 11) bis glutarate (2, 2, 6, 6-tetramethylpiperidine-4-yle) 12) bis adipate (2, 2, 6,

   6-tetramethylpiperidine-4-yl) 13) bis sebacate (2, 2, 6, 6-tetramethylpiperidine-4-yle) 14) bis sebacate (1, 2, 2, 6, 6-pentamethylpiperidine-4-yle) 15) bis (1,2,3,6-tetramethyl-2,6-diethylpiperidine-4-yl) sebacate 16) bis (1-allyl-2,2,6,6-tetramethylpiperidine- phthalate)
4-yle)
 EMI40.2
 17) 1-hydroxy-4-ss-cyanoethoxy-2, 2, 6, 6-tetramethylpiperidine 18) 1-acetyl-2, 2, 6, 6-tetramethylpiperidine-4-yle acetate 19) tris trimellated (2,2 , 6,6-tetramethylpiperidine-4-yl) 20) 1-acroyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine 21) bis (2,2,6,6-tetramethylpiperidine) diethylmalonate
4-yl) 22) bis dibutylmalonate (1,2, 2,6, 6-pentamethylpiperidine-
4-yle) 23) butyl (3, 5-di-tert-butyl-4-hydroxybenzyl)

     bis (1,2,2,6,6-pentamethylpiperidine-4-yl) malonate 24) bis (1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl) sebacate 25) sebacate bis (1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidine-4-yl)

  <Desc / Clms Page number 41>

 26) hexane-1 ', 6'-bis (4-carbamoyloxy-1-n-butyl-2,2,6,6- tetramethylpiperidine) 27) toluene-2', 4'-bis (4-carbamoyloxy-1- n-propyl-2,2,6,6- tetramethylpiperidine) 28) dimethyl-bis (2,2,6,6-tetramethylpiperidine-4-oxy) silane 29) phenyl-tris (2,2,6,6-tetramethylpiperidine -4-oxy) silane 30) tris phosphite (1-propyl-2, 2,6, 6-tetramethyl-piperidine-4-yl) 31) tris phosphate (1-propyl-2, 2,6, 6- tetramethyl-piperidine-4-yl) 32) bis phenylphosphonate (1,2, 2,6,

   6-pentamethyl-piperidine-4-yl) 33) 4-hydroxy-1,2,2,6,6-pentamethylpiperidine 34) 4-hydroxy-N-hydroxyethyl-2, 2,6, 6-tetramethylpiperidine 35) 4- hydroxy-N- (2-hydroxypropyl) -2, 2,6, 6-tetramethylpiperidine 36) 1-glycidyl-4-hydroxy-2, 2,6, 6-tetramethylpiperidine.



  (b ') Compounds of formula XIIb
 EMI41.1
 where n is the number 1 or 2,
G, G1 and G11 are as defined in (a '),
 EMI41.2
 G13 is hydrogen, a C alkyl group <-C, C-Cc hydroxyalkyl, Cr-Cy cycloalkyl, Cy-Cg aralkyl, C-Cg alkanoyy, C-Cc alkenoyy, benzoyl or a group of formula
 EMI41.3
 

  <Desc / Clms Page number 42>

 and, if n is 1,
G14 is hydrogen, C1-C1alkyl, C3-C8 alkenyl, Ce-Cy cycloalkyl or C1-C4 alkyl substituted with hydroxyl, cyano, alkoxycarbonyl or carbamide;

   a glycidyl group or a group of formula -CH2-CH (OH) -Z or of formula-CONH-Z, where Z is hydrogen or a methyl or phenyl group, and if n is 2,
G14 is a C-C alkylene group, a C6-C12 arylene group, a xylylene group, a group
 EMI42.1
 - CH-CH (OH) -CH- or a group -CH2-CH (OH) -CH2-0-D-0- where D is a C 1 -C alkylene group.

   , C-Ce arylene, C6-C12 cycloalkylene or, provided that G13 is not an alkanoyl, alkenoyl or benzoyl group, G14 may also be a C2-C12 1-oxo-alkylene group, a divalent radical of a dicarbamic acid or an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or may also be the group - CO-, or else, if n is 1,
G13 and G14 can together form the radical
 EMI42.2
 divalent of an aliphatic, cycloaliphatic or aromatic 1, 2- or 1, 3-dicarboxylic acid.



  Any C1-C12 or Cl-Cl alkyl substituent. is as already defined in (a ').



  Any C-C7 cycloalkyl substituent is in particular a cyclohexyl group.



   If G13 is a Cy-Cg aralkyl group, it is in particular a phenylethyl or in particular benzyl group.



  If G13 is a C2-C5 hydroxyalkyl group, it is in particular a 2-hydroxyethyl or 2-hydroxypropyl group.



   If G13 is a C2-C18 alkanoyl group, it is for example a propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl group, and if G13 is a C3-C5 alkenoyl group, it is including an acroyl group.



   If G14 is a C2-C8 alkenyl group, it is for example an allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl group.

  <Desc / Clms Page number 43>

 



   If G14 is a C1-C4 alkyl group substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide group, it can be, for example, a 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2 -ethoxycarbonylethyl, 2-aminocarbonylpropyl
 EMI43.1
 or 2- (dimethylaminocarbonyl) ethyl.



  Any C2-C12 alkylene substituent is, for example, an ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene group.



   Any arylene substituent in C 1 -C 6 is, for example, a group 0-, m- or p-phenylene, 1, 4-naphthylene or 4,4'diphenylene.



   As the C6-C12 cycloalkylene group, mention is made in particular of the cyclohexylene group.



   Preference is given to the compounds of formula XIIb in which n is 1 or 2, G is hydrogen, G11 is hydrogen or a methyl group, G13 is hydrogen,
 EMI43.2
 a C1-C12 alkyl group or a group of formula
 EMI43.3
 
 EMI43.4
 and G14, if n = 1, is hydrogen or a C1-C12 alkyl group and, if n = 2, is a C2-C8 alkylene group or 1-C-C8 oxo-alkylene.



  Examples of polyalkylpiperidines of this category are the following compounds: 37) N, N'-bis (2, 2, 6, 6-tetramethylpiperidine-4-yl) hexamethylene-1, 6-diamine 38) N, N'-bis (2, 2, 6, 6-tetramethylpiperidine-4-yl) hexamethylene-1, 6-diacetamide 39) bis (2, 2, 6, 6-tetramethylpiperidine-4-yl) amine 40) 4-benzoylamino-2, 2 , 6, 6-tetramethylpiperidine 41) N, N'-bis (2, 2, 6, 6-tetramethylpiperidine-4-yl) N, N'-dibutyladipamide

  <Desc / Clms Page number 44>

 42) N, N'-bis (2,2, 6, 6-tetramethylpiperidine-4-yl) -
N, N'-dicyclohexyl-2-hydroxypropylene-1, 3-diamine 43) N, N'-bis (2,2, 6, 6-tetramethylpiperidine-4-yl) -p-xylylene-diamine
 EMI44.1
 44) N, N'-bis (2, 2, 6, 6-tetramethylpiperidine-4-yl) succinamide 45) N- (2, 2, 6, 6-tetramethylpiperidine-4-yl)

   -ss-aminodipropionate bis (2, 2, 6, 6-tetramethylpiperidine-4-yl) 46) The compound of formula
 EMI44.2
 
 EMI44.3
 47) 4- (bis-2-hydroxyethylamino) -1, 2, 2, 6, 6-pentamethyl- piperidine 48) 4- (3-methyl-4-hydroxy-5-tert-butylbenzamido) -2,2,6 , 6- tetramethylpiperidine 49) 4-methacrylamido-1,2, 2,6, 6-pentamethylpiperidine (c ') Compounds of formula XIIc
 EMI44.4
 
 EMI44.5
 in which n is the number 1 or 2, G, G1 and G11 are as defined in (a ') and, if n is 1, Gl. is a C-Cg alkylene or C-Cg hydroxyalkylene or C-C acyloxyalkylene group, and if n is 2, G15 is the group (-CH2) 2C (CH2-) 2.



  If G1S is a Cp-Cg alkylene or C-Cg hydroxyalkylene group, it is for example an ethylene, 1-methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene group.

  <Desc / Clms Page number 45>

 
 EMI45.1
 



  If G15 is an acyloxyalkylene group at C.-C, it is for example the radical 2-ethyl-2-acetoxymethylpropylene.



  Examples of polyalkylpiperidines in this category are the following compounds: 50) 9-aza-8, 8, 10, 10-tetramethyl-1, 5-dioxaspiro 5] undécan e 51) 9-aza-8, 8, 10, 10 -tetramethyl-3-ethyl-1, 5-dioxaspiro- [5. 5] undecane 52) 8-aza-2, 7, 7, 8, 9, 9-hexamethyl-1, 4-dioxaspiro [4. 5] decane 53) 9-aza-3-hydroxymethyl-3-ethyl-8, 8, 9, 10, 10-pentamethyl- 1, 5-dioxaspiro [5. 5] undecane 54) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8, 8, 10, 10tetramethyl-1, 5-dioxaspiro [5. 5] undecane 55) 2, 2, 6, 6-tetramethylpiperidine-4-spiro-2'- (1 ', 3'- 11 dioxane) -5'-spiro-5 "- (1", 3 "-dioxanne) -2 "-spiro- 4" '- (2 "', 2" ', 6 "', 6" '- tetramethylpiperidine).



  (d ') Compounds of formulas XIId, XIIe and XIIf, the compounds of formula XIIf being preferred
 EMI45.2
 

  <Desc / Clms Page number 46>

 where n is the number 1 or 2,
G, G1 and G11 are as defined in (a '),
G16 is hydrogen or a C1-Cl2 alkyl group,
 EMI46.1
 allyl, benzyl, glycidyl or C-C6 alkoxyalkyl, and if n is 1, G17 is hydrogen, C1-Cl2 alkyl, C-Cr alkenyl, Cy-Cq aralkyl, Cs-C7 cycloalkyl ' CC 4 hydroxyalkyl, C 6 -C alkoxyalkyl, C 6 -C 10 aryl, glycidyl, or a group of formula- - (CH2) p-COO-Q or of formula- (CH) -O-CO-Q, where p is 1 or 2 and Q is a C1-C4 alkyl or phenyl group, and if n is 2,

   
 EMI46.2
 G17 is a C-C alkylene group <, C4-C12 alkenylene C6-Cl2 arylene, a -CH2-CH (OH) -CH2-0-DO-CH2-CH (OH) -CH2- group where D is a C-Co alkylene group , arylene in Cg-C <e, Cc-C cycloalkylene, or a group - CH2CH (OZ ') CH2- (OCH2-CH (OZ') CH2) 2- where Z is hydrogen 2 2) 2- 0 'or an alkyl group in C1-C18, allyl, benzyl, alkanoyl in C2-C12 or benzoyl,
T1 and T2 are each, independently of the other, hydrogen, a C1-C18 alkyl group or a C6-C10 aryl or C7-C9 aralkyl group unsubstituted or substituted
 EMI46.3
 by one or more halogens or C1-C4 alkyl groups, or else T1 and T2, with the carbon atom to which they are attached, form a cycloalkane ring in Ce-C14.



  Any C1-C12 alkyl substituent is, for example, a methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl group. n-decyl, n-undecyl or n-dodecyl.



   Any substituent defined as a C1-C18 alkyl group may be, for example, one of the groups listed above and also, for example, an n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl group.



   Any C2-C6 alkoxyalkyl substituent is, for example, a methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl group,

  <Desc / Clms Page number 47>

 n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl or propoxypropyl.



   If G17 is a C-Ce alkenyl group, it is for example a 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl group.
 EMI47.1
 



  If G, y, T. or T2 is a C-Cq aralkyl group, it is in particular a phenethyl or in particular benzyl group. If T1 and T2, with the carbon atom, form a cycloalkane ring, this can be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.



   If G17 is a C2-C4 hydroxyalkyl group, it is for example a 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl group.



   If G17, T1 or T2 is a Cg-C aryl group, it is in particular a phenyl, alpha- or ss-naphthyl group which is unsubstituted or is substituted by one or more halogens or C1-alkyl groups C4.



   If G17 is a C2-C12 alkylene group, it is for example an ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene group.



   If G17 is a C4-C12 alkenylene group, it is in particular a 2-butenylene, 2-pentenylene or 3-hexenylene group.



   If G17 is a C6-C12 arylene group, it is for example an o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene group.



   If Z is a C2-C12 alkanoyl group, it is for example a propionyl, butyryl, octanoyl, dodecanoyl group, but preferably acetyl.
 EMI47.2
 



  D representing a C 1 -C alkylene group. o, arylene in Cg-C <c or C6-C12 cycloalkylene is as defined in (b ').



   Examples of polyalkylpiperidines in this category are the following compounds:

  <Desc / Clms Page number 48>

 56) 3-benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro [4. 5] - decane-2,4-dione 57) 3-n-octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro zu décane-2,4-dione 58) 3-allyl-1 , 3, 8-triaza-1, 7,7, 9, 9-pentamethylspiro [4. 5] - decane-2,4-dione 59) 3-glycidyl-1, 3,8-triaza-7, 7,8, 9, 9-pentamethylspiro- [4. 5] decane-2,4-dione 60) 1, 3, 7, 7,8, 9,9-heptamethyl-1, 3, 8-triazaspiro [4. 5] decane-
2,4-dione 61) 2-isopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4. 5] decane
 EMI48.1
 62) 2, 2-dibutyl-7, 7, 9, 9-tetramethyl-1-oxa-3, 8-diaza-4-oxo-spiro [4.

   5] decane 63) 2,2, 4, 4-tetramethyl-7-oxa-3, 20-diaza-21-oxodispiro- [5. 1.11. 2] henicosan 64) 2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxospiro- [4. 5] decane, and preferably 65) 8-acetyl-3-dodecyl-1, 3,8-triaza-7, 7,9, 9-tetramethylspiro [4. 5] decane-2, 4-dione and the compounds of the following formulas:

   
 EMI48.2
 

  <Desc / Clms Page number 49>

 
 EMI49.1
 (e ') Compounds of formula XIIg, which are themselves preferred,
 EMI49.2
 where n is the number 1 or 2 and
G18 is a group of one of the formulas
 EMI49.3
 
 EMI49.4
 where G and G11 are as defined in (a '), G1 and G2 are hydrogen or a methyl group or together form a substituent = 0,
E is -O- or -NG13-,
A is a C2-C6 alkylene group or - (CH2) 3-O-, x is the number 0 or 1,
G13 is hydrogen or a C1-C12 alkyl, C-Cc hydroxyalkyl or C5-C7 cycloalkyl group,

  <Desc / Clms Page number 50>

 
 EMI50.1
 G19 is identical to G18 or is one of the groups - NGG, -OG, -NHCHOG or-N (CHOG),
G20, if n = 1, is identical to G18 or G19 and, if n = 2, G20 is a group-E-B-E-,

   where B is a C2-C8 alkylene group or a C-Cg alkylene group which is interrupted by 1 or 2 -N (G21) - groups,
G21 is a C alkyl group <-C, cyclohexyl, benzyl or C1-C4 hydroxyalkyl or a group of formula
 EMI50.2
 or a group of formula
 EMI50.3
 
G22 is C1-C12 alkyl, cyclohexyl, benzyl or C1-C4 hydroxyalkyl, or G21 and G22 together form a C4-CS alkylene or oxa-alkylene group
 EMI50.4
 C.-Cc, for example-CHCHOCHCH-, or a group of formula - CHCHN (G) CHCH-, and
G23 is hydrogen, a C1-C12 alkyl group or a phenyl group.



   Any C1-C12 alkyl substituent is, for example, a methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl group. n-decyl, n-undecyl or n-dodecyl.



   Any C2-C5 hydroxyalkyl substituent is, for example, a 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl group.



   If A is a C2-C6 alkylene group, it is for example an ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene group.

  <Desc / Clms Page number 51>

 



   If G21 and G22 together form a C4-C5 alkylene or oxa-alkylene group, this is, for example, a tetramethylene, pentamethylene or 3-oxapentamethylene group.



   Examples of polyalkylpiperidines in this category are the compounds of the following formulas:
 EMI51.1
 

  <Desc / Clms Page number 52>

 
 EMI52.1
 R is defined as for compound 74.

  <Desc / Clms Page number 53>

 
 EMI53.1
   Is defined as for compound 76.
 EMI53.2
 

  <Desc / Clms Page number 54>

 
 EMI54.1
 (f ') Oligomeric or polymeric compounds whose recurring structural unit contains a radical of 2,2,6,6-tetraalkylpiperidine, in particular polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly (meth) acrylates, poly (meth) acrylamides and their copolymers which contain these radicals.



   Examples of 2,2, 6, 6-polyalkylpiperidines in this category are the compounds of the following formulas, in which m is a number from 2 to about 200.
 EMI54.2
 

  <Desc / Clms Page number 55>

 
 EMI55.1
 

  <Desc / Clms Page number 56>

 
 EMI56.1
 

  <Desc / Clms Page number 57>

 
 EMI57.1
 

  <Desc / Clms Page number 58>

 
 EMI58.1
 where R is a group of formula
 EMI58.2
 
 EMI58.3
 R or is a chain branch- (CH) -N- each of - (CH2) i- N -MI '
 EMI58.4
 me and m "is an integer between 0 and 200, provided that m '+ m" = m.



   Other examples of polymeric compounds are the reaction products of compounds of formula
 EMI58.5
 with epichlorohydrin; polyesters of butane-1,2,3,4-tetracarboxylic acid with a bifunctional alcohol of formula
 EMI58.6
 whose side carboxylic chains from tetracarboxylic acid are esterified with 2,2,6,6-tetramethyl-4-hydroxypiperidine;

  <Desc / Clms Page number 59>

 the compounds of formula
 EMI59.1
 where about a third of the radicals R are -C2H5 and the rest are
 EMI59.2
 
 EMI59.3
 and m is a number in the range of 2 to 200;

   or the copolymers of which the recurring motif consists
 EMI59.4
 CHg of two patterns /. \ -C == CH, and in each case an OO (C) motif and an oVo motif. and an oVo! H- JLCHs u 13 H C N CH3 1 H (g ') Compounds of formula XIIIa
 EMI59.5
 where n is the number 1 or 2,
G and G11 are as defined in (a '), and
G14 is as defined in (b '), the values-CONH-Z and -CH2-CH (OH) -CH2-O-D-O- being excluded for G14.

  <Desc / Clms Page number 60>

 



  Examples of these compounds are:
 EMI60.1
 
Particularly advantageous compositions are those which contain, as component (e), at least one compound of one of the formulas H1, H2, H3, H4, H5, H6 and H7
 EMI60.2
 

  <Desc / Clms Page number 61>

 
 EMI61.1
 

  <Desc / Clms Page number 62>

 
 EMI62.1
 
 EMI62.2
 in which m is a number between 2 and 200.



  The component (e) of the new composition, or the sterically hindered amine compounds, are known and some are commercially available.



  Tinuvin123, Tinuvin144, Tinuvin292, Tinuvin622, Chimassorb944 and Chimassorb119 are protected trademarks of Ciba Spezialitâtenchemie AG.



  Particular preference is given to the addition, as component (e) of the new composition, of sterically hindered amines whose molecular weight or average molecular weight Mn is in the range of 500 to 10,000, particularly in the range of 1,000 to 10,000.



  Among these, it also particularly retains sterically hindered amines whose molecular weight or average molecular weight Mn is in the range from 1500 to 10,000, for example in the range from 2000 to 7500.



  Special mention must be made of new compositions which contain, as component (e), two or more hindered amine type compounds.



  The mixture of components (b), (c), (d) and (e) is suitable for stabilizing organic materials against degradation caused by oxidation, heat or light. Examples of these materials are:

  <Desc / Clms Page number 63>

 
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins such as cyclopentene or norbornene, polyethylene (which may optionally be crosslinked), for example high density polyethylene (HDPE), high molecular weight high density polyethylene (HDPE-PME), ultra high molecular weight high density polyethylene (HDPE) -PMUE), medium density polyethylene (PEMD),

   low density polyethylene (LDPE), linear low density polyethylene (LDPE), very low density polyethylene (PETBD) and ultra low density polyethylene (PEUBD).



   The polyolefins, that is to say the polymers of monoolefins illustrated by examples in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by various processes, and in particular those which follow: a) radical polymerization (normally under high pressure and at high temperature). b) Catalytic polymerization using a catalyst which normally contains one or more metals from Groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more ligands, typically oxides, halides, alcoholates, esters, ethers, amines, alkyl groups, alkenyl groups and / or aryl groups which can be coordinated by n or a bonds.

   These metal complexes can be in the free form or be fixed on substrates, typically on an activated form of magnesium chloride, titanium-III chloride, alumina or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be used in isolation in the polymerization or else other

  <Desc / Clms Page number 64>

 activators, typically alkylmetals, metal hydrides, alkylmetal halides, alkylmetal oxides or alkylmetaloxanes, said metals being elements of Groups Ia, IIa and / or IIIa of the Periodic Table. The activators can be suitably modified with additional ester, ether, amine or silyl group.



   These catalytic systems are usually called Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (Du Pont), metallocenes or monosite catalysts (SSC).



   2. Mixtures of the polymers mentioned in 1), for example mixtures of polypropylene and polyisobutylene, polypropylene and 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 (LDPE) and its mixtures with low density polyethylene (LDPE), propylene copolymers / but-1-ene, propylene / isobutylene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene copolymers / butadiene, 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 ethylene terpolymers with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of these copolymers with one another and with the polymers mentioned in 1) above, for example polypropylene / ethylene-propylene copolymer blends,

  <Desc / Clms Page number 65>

 LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LDPE / EVA and PEBDL / EAA, and alternating or random polyalkylene / carbon monoxide copolymers and their blends with other polymers , for example polyamides.



   4. Hydrocarbon resins (eg Ce-Cg), including their hydrogenated modification products (eg tackifiers), and mixtures of polyalkylenes and starch.



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



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



   7. Grafted copolymers of styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene / propylene / diene terpolymers;

   styrene and acrylonitrile on polyalkyl acrylates or polymethylmethacrylates, styrene and acrylonitrile on

  <Desc / Clms Page number 66>

 acrylate / butadiene copolymers, as well as their blends with the copolymers listed in 6), for example blends of copolymers known as ABS, MBS, ASA or AES polymers.



   8. Halogenated polymers such as polychloroprene, chlorinated rubbers, a chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, homo- and epichlorohydrin copolymers, in particular polymers of halogenated vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as their copolymers such as vinyl chloride / chloride copolymers vinylidene, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate.



   9. Polymers which are derived from unsaturated acids in a, ss and their derivatives, such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles modified with butyl acrylate to improve impact resistance.



   10. Copolymers of the monomers mentioned in 9) with one another or with other unsaturated monomers, for example acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymers or the acrylonitrile / alkyl methacrylate / butadiene terpolymers.



   11. Polymers which are derived from unsaturated alcohols and amines, or their acylated derivatives or their acetals, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinylbutyral, polyallyloulapolyallylmelamine phthalate; as well as their copolymers formed with the olefins mentioned in 1) above.



   12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, poly (ethylene oxide),

  <Desc / Clms Page number 67>

 poly (propylene oxide) or their copolymers formed with bisglycidyl ethers.



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



   14. Phenylene polyoxides and polysulphides and mixtures of phenylene polyoxides with styrenic polymers or polyamides.



   15. Polyurethanes which are derived, on the one hand, from polyethers, polyesters or polybutadienes having terminal hydroxyl groups, and, on the other hand, from aliphatic or aromatic polyisocyanates, as well as their precursors.



   16. Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and / or amino carboxylic acids or corresponding lactams, for example polyamide 4, polyamide 6, polyamides 6-6,6-10, 6 -9, 6-12,4-6, 12-12, polyamide 11, polyamide 12, aromatic polyamides prepared from m-xylylenediamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic and / or 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 above-mentioned polyamides with polyolefins, olefinic copolymers, ionomers or elastomers chemically linked or grafted, or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified by EPDM or ABS; and polyamides condensed during processing (R.I.M systems for polyamides).



   17. Polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.



   18. Polyesters which are derived from dicarboxylic acids and diols and / or hydroxy carboxylic acids

  <Desc / Clms Page number 68>

 or corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyetheresters derived from polyethers having terminal hydroxyl groups; and also polyesters modified with polycarbonates or MBS.



   19. Polycarbonates and polyestercarbonates.



   20. Polysulfones, polyethersulfones and polyetherketones.



   21. Crosslinked polymers which are 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 which are derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyalcohols and vinyl compounds as crosslinking agents, and also their halogenated modification products with low flammability.



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



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



   26. Crosslinked epoxy resins which are derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidylated compounds, for example the products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked by usual hardeners such as anhydrides or amines, with or without accelerators.



   27. Natural polymers such as cellulose, rubber, gelatin and their chemically modified homologous derivatives, for example cellulose acetates,

  <Desc / Clms Page number 69>

 cellulose propionates and cellulose butyrates, or cellulose ethers such as methylcellulose; as well as rosins and their derivatives.



   28. Blends of the above polymers, 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 / PUR thermoplastic, PC / PUR thermoplastic, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6-6 and copolymers, PA / PEHD, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.



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



   30. Aqueous emulsions of natural or synthetic rubber, for example natural latex or latexes of carboxylated styrene / butadiene copolymers.



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



   Polyurethanes are obtained, for example, by reacting polyethers, polyesters and polybutadienes which contain terminal hydroxyl groups with aliphatic or aromatic polyisocyanates.



   Polyethers having terminal hydroxyl groups are known and are prepared, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran,

  <Desc / Clms Page number 70>

 styrene oxide or epichlorohydrin with themselves, for example in the presence of Bizou by an addition reaction of these epoxides, alone or in mixture or successively, with starting components containing reactive hydrogen atoms, such as water, alcohols, ammonia or amines, for example ethylene glycol, propylene-1, 3 and 1, 2-glycols, trimethylolpropane, 4,4'-dihydroxydiphenylpropane, aniline , ethanolamine or ethylenediamine. The sucrose polyethers are also suitable according to the invention.

   In many cases, preference is given to polyethers which mainly contain primary OH groups (up to 90% by weight, relative to all of the OH groups present in the polyether).



  In addition, polyethers modified by vinyl polymers, such as those formed for example by polymerizing styrene and acrylonitrile in the presence of polyethers, are suitable, as are polybutadienes containing OH groups.



   These compounds generally have molecular weights of 400 to 10,000 and are polyhydroxy compounds, in particular compounds containing two to eight hydroxyl groups, in particular those whose molecular weight is from 800 to 10,000, preferably 1000 to 6000, for example polyethers containing at least 2, generally 2 to 8, but preferably 2 to 4 hydroxyl groups, as they are known per se for the preparation of homogeneous polyurethanes and cellular polyurethanes.



   It is obviously possible to use mixtures of the above compounds containing at least two hydrogen atoms reactive with isocyanates, in particular having a molecular weight of 400 to 10,000.



   Suitable polyisocyanates are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-diisocyanatododecane, 1,3-diisocyanato-cyclobutane, 1, 3- and

  <Desc / Clms Page number 71>

 1,4-diisocyanato-cyclohexanes and also any desired mixtures of these isomers, 1-isocyanato-3, 3,5trimethyl-5-isocyanatomethylcyclohexane, diisocyanates of hexahydro-2, 4- and-2, 6- tolylene and also any desired mixtures of these isomers, diisocyanates of hexahydro-1, 3-and / or-1, 4-phenylene, diisocyanates of perhydro-2, 4'-and / or-4, 4 '-methylenediphenyl,

     diisocyanates of 1, 3- and 1,4-phenylene, diisocyanates of 2, 4- and 2,6-tolylene, and also any desired mixtures of these isomers, diisocyanates of 2, 4'- and / or 4,4'methylenediphenyl, 1,5-naphthylene diisocyanate,
 EMI71.1
 4, 4 ', isocyanato-triphenylmethane, polyphenyl-polymethylene polyisocyanates obtained by condensation of aniline-formaldehyde, then phosgenation, m- and p-isocyanatophenylsulfonyl isocyanates, aromatic perchlorinated polyisocyanates, polyisocyanates containing carbodiimide groups, polyisocyanates containing allophanate groups, polyisocyanates containing isocyanurate groups, polyisocyanates containing urethane groups, polyisocyanates containing acylated urea groups, polyisocyanates containing biuret groups,

   polyisocyanates containing ester groups, reaction products of the aforementioned isocyanates with acetals, and polyisocyanates containing radicals of polymeric fatty acids.



  * It is also possible to use the distillation residues containing isocyanate groups, as such or dissolved in one or more of the polyisocyanates mentioned above, which are obtained during the industrial preparation of isocyanates. It is further possible to use any desired mixtures of the above polyisocyanates.



   In general, particular preference is given to polyisocyanates which can be easily obtained industrially, for example 2, 4 and 2,6-tolylene diisocyanates and any desired mixtures of these.

  <Desc / Clms Page number 72>

 isomers ("TDI"), polyphenyl polyethylene polyisocyanates as prepared by condensation of aniline formaldehyde, then phosgenation ("crude MDI"), and polyisocyanates containing carbodiimide, urethane, allophanate, isocyanurate, urea or biuret groups ("modified polyisocyanates ").



   The organic materials to be protected are preferably natural, semi-synthetic or, in particular, synthetic polymers. Thermoplastic polymers are particularly preferred, in particular polyolefins, in particular polyethylene and polypropylene or their copolymers with mono and diolefins.



   Particular emphasis should be placed on the action of the new compounds against degradation by heat and oxidation, in particular under thermal stresses as encountered during the use of thermoplastic materials. The new components (b), (c), (d) and (e) are therefore remarkably suitable for being used as processing stabilizers (in processing operations).



   The mixture of components (b), (c), (d) and (e) is also suitable for stabilizing polyolefins which are subjected to long-term contact with media with extractive action.



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



   Components (c), (d) and (e) are suitably added to the organic material to be stabilized in an amount of 0.01 to 10%, for example from 0.01 to 5%, preferably from 0.025 to 3% and in particular from 0.025 to 1%, relative to the weight of the organic matter to be stabilized.



   In addition to components (a), (b), (c), (d) and (e), the new compositions may include other co-stabilizers (additives), for example the following:

  <Desc / Clms Page number 73>

 1. Antioxidants 1.1. Alkylated monophenols, for example: 2,6-di-tert-butyl-
 EMI73.1
 4-methylphenol, 2-tert-butyl-4, 6-dimethylphenol, 2, 6-ditert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-n-butylphenol, 2, 6-di- tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (a-methylcyclohexyl) -4, 6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4, 6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2,6-dinonyl-4-methylphenol, 2,4-dimethyl- 6- (1'-methylundéc -1'-yl) phenol, 2,

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



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



  1.3. Hydroquinones and alkylated hydroquinones, for example:
 EMI73.2
 2, 6-di-tert-butyl-4-methoxyphenol, 2, 5-di-tert-butylhydroquinone, 2, 5-di-tert-amylhydroquinone, 2, 6-diphenyl-4-octa- decyloxyphenol, 2, 6- di-tert-butylhydroquinone, 2,5-ditert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, adipate bis (3,5-di-tert-butyl-4-hydroxyphenyl).



  1.4. Tocopherols, for example: a-tocopherol, ss-tocopherol, y-tocopherol, 8-tocopherol and their mixtures (Vitamin E).



  1.5. Hydroxylated diphenyl thioethers, for example: 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis- (4-octylphenol), 4,4'-thiobis (6-tert- butyl-3-methylphen01),
 EMI73.3
 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis- (3,6-di-sec-amylphenol), disulfide of 4,4'-bis (2, 6- dimethyl-4-hydroxyphenyl).



  1.6. Alkylidene-bisphenols, for example: 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis- (6-tert-butyl-4-ethylphenol), 2,2 ' -methylene-bis [4-methyl- 6- (a-methylcyclohexyl) phenol], 2,2'-methylene-bis (4-methyl- 6-cyclohexylphenol), 2, 2'-methylene-bis (6-nonyl- 4-methyl-

  <Desc / Clms Page number 74>

 phenol), 2,2'-methylene-bis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-ethyli-
 EMI74.1
 dene-bis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (a-methylbenzyl) -4-nonylphenol], 2,2'-methylene-bis- [6- (a, <x-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4 '-methylene-bis (6-tertbutyl-2-methylphenol), 1, 1 -bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane,

   2, 6-bis (3-tert-butyl-5-methyl- 2-hydroxybenzyl) -4-methylphenol, 1,1, 3-tris (5-tert-butyl- 4-hydroxy-2-methylphenyl) butane, 1 , 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, bis [3, 3-bis (3'-tert-butyl-4'-hydroxyphenyl) ethylene butyrate -glycol, bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6- terephthalate tert-butyl-4-methyl-phenyl], 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane,
 EMI74.2
 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercapto- butane, 1.1, 5,

  5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.



  1.7. 0-, N- and S-benzylated compounds, for example: 3, 5, 3 ', 5'-
 EMI74.3
 tetra-tert-butyl-4, 4'-dihydroxy (dibenzyl oxide), 4-hydroxy-3, 5-dimethylbenzylthioglycolated'octadecyl, 4-hydroxy-3, 5-di-tert-butylbenzylthioglycolate, tris (3, S-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4 sulfide) -hydroxybenzyle), 3,5-ditert-butyl-4-hydroxybenzylthioglycolate of isooctyl.



  1.8. Hydroxybenzylated malonates, for example: 2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) dioctadecyl malonate,
 EMI74.4
 2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) dioctadecyl malonate, 2, 2-bis (3, S-di-tert-butyl-4-hydroxybenzyl) didodecylmercaptoethyl malonate, 2, 2-bis (3,5 (di-tert-butyl-4-hydroxybenzyl) bis [4- (1,1,3,3-tetramethylbutyl) phenyl) malonate.



  1.9. Aromatic hydroxybenzyl compounds, for example: 1, 3,5-tris (3, S-di-tert-butyl-4-hydroxybenzyl) -2, 4, 6-tri-

  <Desc / Clms Page number 75>

 methylbenzene, 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 (octyl-mercapto) -6- (3, 5-di-tert-butyl-4-hydroxyanilino) -1, 3,5triazine, 2-octylmercapto-4,6-bis (3, 5-di-tert-butyl-
 EMI75.1
 4-hydroxyanilino) -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-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris isocyanurate (3,5-di-tert-butyl- 4- hydroxybenzyl), 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4- hydroxyphenylethyl) -1, 3,5-triazine, 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro- 1,3,5-triazine, 1,3 isocyanurate , 5-tris (3,5-dicyclohexyl-4-hydroxybenzyl).



  1.11. Benzylphosphonates, for example: 2,5-di-tert-butyl-
 EMI75.2
 Dimethyl 4-hydroxybenzylphosphonate, 3,5-di-tert-butyl- 4-hydroxyethylbenzylphosphonate, 3,5-di-tert-butyl- 4-hydroxybenzylphosphonate dioctadecyl, 5-tert-butyl- 4-hydroxy-3- dioctadecyl methylbenzylphosphonate, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.
 EMI75.3
 



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



  1. 13. Esters of ss- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono or polyalcohols, for example with methanol, ethanol, n-octanol , isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thia-undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl - 1-phospha-2,6, 7-trioxabicyclo [2. 2.2] octane.

  <Desc / Clms Page number 76>

 



  1. 14. Esters of ss- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono or polyalcohols, for example with methanol, ethanol, n-octanol , isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentylglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thia-undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl -
 EMI76.1
 1-phospha-2, 6, 7-trioxaoicyclo [2. 2.2] octane.



  1. 15. P- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid esters with mono or polyalcohols, for example 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, l tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thia-undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6 , 7-trioxabicyclo- [2. 2.2] octane.



  1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono or polyalcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6hexanediol, 1,9-nonanediol, ethylene glycol, 1,2propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris isocyanurate (hydroxyethyl ), N, N'bis (hydroxyethyl) oxamide, 3-thia-undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2. 2.2] octane.



  1.17. Amides of ss- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example: N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -

  <Desc / Clms Page number 77>

 
 EMI77.1
 trimethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide, N, N'-bis [2- (3- [3, 5-di-tert-butyl- 4- hydroxyphenyl] propionyloxy) ethyl] oxamide (NaugardxL-1 supplied by Uniroyal).



  1.18. Ascorbic acid (vitamin C) 1.19. Amino antioxidants, for example: N, N'-diisopropyl-
 EMI77.2
 p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1, 4-dimethylpentyl) -p-phenylenediamine, N, N'-bis- (1-ethyl-3 -methylpentyl) -p-phenylenediamine, N, N'-bis- (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl- p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine,
 EMI77.3
 N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropylN'-phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) N'-phenyl-p-phenylenediamine, N- (1- methylheptyl) -N'-phenylp-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylene-diamine, 4- (p-toluene-sulfamoyl) diphenylamine, N, N'-dimethylN, N'-di-sec- butyl-p-phenylenediamine,

     diphenylamine,
 EMI77.4
 N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl- 1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine such as p, p'-di- tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2, 6-di-tert-butyl-4-dimethylamin 4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis-
 EMI77.5
 [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, N-phenyl-1- naphthylamine <:

   er & -octylée, mixture of ert: -butyl / tert-octyldiphenylamines mono- and dialkylated, mixture of nonyldiphenylamines mono- and dialkylated, mixture of dodecyldiphenylamines mono- and dialkylated, mixture of isopropyl / isohexyldiphenylamines mono-and dialkylated -butyldiphenylamines mono and dialkylated, 2,3-dihydro-3,3-dimethyl-4H-1, 4-benzothiazine, phenothiazine, mixture of tert-butyl / tert-octylphenothiazines mono and dialkylated, mixture of tert-octylphenothiazines mono- and dialkylated,

  <Desc / Clms Page number 78>

 
 EMI78.1
 N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1, 4-diaminobut-2-ene, N, N-bis (2, 2, 6, 6-tetramethylpiperid-4-yl) hexamethylenediamine, sebacate bis (2, 2, 6, 6-tetramethylpiperid-4-yle), 2, 2, 6, 6-tetramethylpiperidin-4-one, 2, 2, 6,

   6-tetramethylpiperidine-4-ol.



  2. UV absorbers and light stabilizers 2. 1. 2- (2'-hydroxyphenyl) benzotriazoles, for example: 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5 '-ditert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl- 2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'- (1, 1, 3, 3tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-tertbutyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tertbutyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-ditert- amyl-2'-hydroxyphenyl) benzotriazole, 2- 5'-bis- (a, a-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'tert-butyl-2'-hydroxy-5'- (2 -octyloxycarbonylethyl) phenyl) - 5-chlorobenzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl)

   -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy- 5'- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-terbutyl-2'-hydroxy-5'- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5'- [2- (2-ethylhexyloxy) carbonyl-ethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl- 2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [3'-tert-bu tyl - 2'-hydroxy-5'- (2-isooctyloxycarbonylethyl) phenyl] benzotriazole, 2, 2'-methylene-bis [4- (1, 1, 3, 3-tetramethylbutyl) - 6-benzotriazole-2-ylphenol]; 2- [3'-tert-butyl-5'- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole transesterification product with polyethylene glycol 300; [R-CH2CH2-COO-CH2CH2-where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazole-2-ylphenyl;

   2- [2'-hydroxy-3'- (a, a-dimethylbenzyl) -5'- (1, 1, 3, 3-tetramethylbutyl) phenyl] benz0triazole, 2- [2'-hydroxy-3'- (1 , 1, 3, 3-tetramethylbutyl) - 5'- (a, a-dimethylbenzyl) phenyl] benzotriazole.

  <Desc / Clms Page number 79>

 2.2. 2-hydroxybenzophenones, for example derivatives carrying substituents 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxy- 4,4'-dimethoxy.



  2.3. Esters of substituted and unsubstituted benzoic acids, for example: 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylrésorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylrésorcinol, 3,5di-tert- 2,4-di-tert-butylphenyl, 3,5-di-tert-butyl-4-hydroxybenzoate, 3,5-di- butyl-4-hydroxybenzoate
 EMI79.1
 octadecyl tert-butyl-4-hydroxybenzoate, 3,5-di-tert-butyl-4-hydroxybenzoate of 4-methyl-4,6-di-tert-butylphenyl.



  2. 4. Acrylates, for example: a-cyano-P. Ethyl p-diphenylacrylate, isooctyl s-diphenylacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-ss-methyl-p-methoxy-cinnamate, a-cyano-ss-methyl- p-methoxycinnamate
 EMI79.2
 butyl, methyl a-carbomethoxy-p-methoxycinnamate and N- (ss-carbomethoxy-ss-cyanovinyl) -2-methylindoline.



  2.5. Nickel compounds, for example: nickel complexes with 2, 2'-thio-bis [4- (1, 1, 3,3-tetramethylbutyl) 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 monoalkyl esters, for example methyl or ethyl ester, 4-hydroxy-3 acid, 5-di-tert-butylbenzylphosphonique, nickel complexes with ketoximes, for example with 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complexes with 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.



  2.6. Sterically hindered amines, for example: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2, 6,6-tetramethyl-4-piperidyl succinate), bis sebacate ( 1,2, 2,6, 6-pentamethyl-4-piperidyl), sebacate
 EMI79.3
 bis (1-octyloxy-2, 2, 6, 6-tetramethyl-4-piperidyl), bis (1, 2, 2, 6, 6pentamethyl) n-butyl- 3, 5-di-tert-butyl- 4-hydroxybenzylmalonate -4-piperidyl), condensation product of the

  <Desc / Clms Page number 80>

 
 EMI80.1
 1 1 1 1 1- (2-hydroxyethyl) -2, 2, 6, 6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N, N'-bis (2,2 , 6, 6-tetramethyl-4-piperidyl) - hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro 1,3, 5-triazine, nitrilotriacetate of tris (2,2, 6,

  6-tetramethyl-4-piperidyl), butane-1,2,3,4,4-tetrakarboxylate (2,2,6,6-tetramethyl-4-piperidyl), 1, 1'- (ethane-1, 2 -diyl) - bis (3,3, 5,5-tetramethylpiperazinone), 4-benzoyl-2,2, 6,6tetramethylpiperidine, 4-stearyloxy-2,2, 6,6-tetramethylpiperidine, 2-n-butyl-2 - (2-hydroxy-3, 5-di-tert-butylbenzyl) - bis (1,2, 2,6, 6-pentamethylpiperidyl) malonate, 3-n-octyl- 7,7, 9,9-tetramethyl- 1, 3, 8-triazaspiro [4.

   5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, linear or cyclic condensation of N, N'bis (2,2, 6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1, 3,5-triazine, product of condensation of 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis- (3-aminopropylamino) ethane, condensation product of 2-chloro-4,6-di (4-n-butylamino-1,2, 2,6, 6-pentamethyl-piperidyl) -1, 3,5-triazine and 1,2 -bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7, 9,9-tetramethyl-1, 3,8triazaspiro [4.

   5] decane-2, 4-dione, 3-dodecyl-1- (2, 2,6, 6tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl- 1- (1, 2,2, 6,6-pentamethyl-4-piperidyl) pyrrolidin-2, 5-dione, mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2, 6, 6-tetramethylpiperidines, condensation product of N, N'-bis - (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1, 3,5-triazine, condensation product of 1,2-bis (3- aminopropylamino) ethane and 2,4,6-trichlor-1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg.

   No [136504-96-6], N- (2, 2,6, 6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1, 2,2, 6, 6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 2-undecyl-7,7, 9, 9-tetramethyl-1-oxa-3, 8-diaza-4-oxospiro- [4. 5] decane, reaction product of 7.7, 9.9-tetramethyl-

  <Desc / Clms Page number 81>

 
 EMI81.1
 2-cycloundecyl-1-oxa-3, 8-diaza-4-oxospiro [4.

   5] decane and epichlorohydrin, 1, 1-bis (1, 2, 2, 6, 6-pentamethyl- 4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethene, N, N'-bisformyl-N, N'-bis (2, 2, 6, 6-tetramethyl-4-piperidyl) hexamethylenediamine, diester of 4-methoxymethylenemalonic acid with 1, 2, 2, 6, 6-pentamethyl-4-hydroxypiperidine, poly [methylpropyl -3-oxy-4- (2, 2, 6, 6-tetramethyl-4-piperidyl)] siloxane, reaction product of a maleic anhydride / a-olefin copolymer with 2, 2, 6, 6-tetramethyl-4 -aminopiperidine or 1, 2, 2, 6, 6-pentamethyl-4-aminopiperidine.



  2. 7. Oxamides, for example: 4, 4'-dioctyloxyoxanilide, 2, 2'-diethoxyoxanilide, 2, 2'-dioctyloxy-5, 5'-di-tertbutbutananide, 2, 2'-didodecyloxy-5, 5 ' -di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2- ethoxy-2'-ethyl-5, 4'-di-tert-butoxanilide, mixtures of orho- and para-dimethoxy-oxanilides and mixtures of o- and p-diethoxy-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-hydroxy-4-octyloxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) - 1, 3, 5-triazine, 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4 -dimethylphenyl) -1, 3, 5-triazine, 2, 4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2- (2- hydroxy- 4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3, 5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) - 4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2- [2-hydroxy- 4 - (2-hydroxy-3-butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3- octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy)

  - 2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] - 4, 6-bis (2, 4-dimethylphenyl) -1, 3, 5-triazine, 2- (2-hydroxy- 4-hexyloxy) phenyl-4, 6-diphenyl-1, 3, 5-triazine, 2- (2 -hydroxy-

  <Desc / Clms Page number 82>

 4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris- [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3 5-
 EMI82.1
 triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl- 1, 3, 5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-oxy ) - 2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl) - 1,3,5-triazine.



  3. Metal deactivators, for example: N, N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis- (salicyloyl) hydrazine, N, N'-bis (3, 5-di- tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalic dihydrazide, oxanilide, isophthalic dihydrazide, sebacic bisphenylhydrazide, N, N'-diacetyldihydrazide adipic, N, N '-bis (salicyloyl) oxalic dihydrazide, N, N'-bis (salicyloyl) dihydrazide thiodipropionic.



  4. Phosphites and phosphonites, for example: triphenyl phosphite, diphenyl and alkyl phosphites, phenyl and dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, diphosphitedistearyl-pentaerythritol, tris phosphite (2,4-di-tert-butylphenyl), diisodecyl-pentaerythritol diphosphite, bis (2,4-di-tertbutylphenyl) -pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl diphosphite) ) -pentaerythritol, diisodecyloxy-pentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) diphosphite) -pentaerythritol, bis (2,4, 6-tris-tert-butylphenyl) diphosphite) -pentaerythritol, tristearyl-sorbitol triphosphit, 4,

     4 '-biphenylene- tetrakis diphosphonite (2,4-di-tert-butylphenyl),
 EMI82.2
 6-isooctyloxy-2, 4, 8, 10-tetra-tert-butyl-12H-dibenzo [d, g] - 1, 3, 2-dioxaphosphocine, 6-fluoro-2, 4, 8, 10-tetra-tert -butyl- 12-methyl-dibenzo [d, g] -1, 3, 2-dioxaphosphocine, bis (2,4-di-tert-butyl-6-methylphenyl) and methyl phosphite, bis (2, 4-di-tert-butyl-6-methylphenyl) and ethyl, 2, 2 ', 2 "-nitrilo [tris (phosphite of 3, 3', 5, 5'- tetra-tert-butyl-1,1 '-biphenyl-2,2'-diyl and ethyl)], phosphite of 3.3', 5,5'-tetra-tert-butyl-1, 1'-biphenyl-2,2'-diyl and of 2-ethylhexyl.

  <Desc / Clms Page number 83>

 5.

   Hydroxylamines, for example: N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, Namine -hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated tallow amine.
 EMI83.1
 



  6. Nitrones, for example: N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecyl-nitrone, N -hexadecyl-alpha-pentadecylnitrone, N-octadecylalpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecylnitrone, N-heptadecylalpha-heptadecylnitrone, N-octadecylnitrone, N-octadecylnitrone dialkylhydroxylamine derived from hydrogenated tallow amine.



  7. Sulfur synergists, for example: dilauryl thiodipropionate or distearyl thiodipropionate.



  8. Compounds eliminating peroxides, for example: esters of ss-thiodipropionic acid such as lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or zinc salt of 2-mercaptobenzimidazole, dibutyldithiocarbamate of zinc, dioctadecyl disulfide, (ss-dodecylmercapto) pentaerythritol propionate.



  9. Stabilizers for polyamides, for example: copper salts in combination with iodides and / or phosphorus compounds and divalent manganese salts.



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

  <Desc / Clms Page number 84>

 
 EMI84.1
 11.

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



  12. Fillers and reinforcing agents, for example: calcium carbonate, silicates, glass fibers, hollow glass beads, asbestos, talc, kaolin, mica, barium sulphate, metal oxides and hydroxides, carbon black, graphite, sawdust wood and flours or fibers from other natural products, synthetic fibers.



  13. Other additives, for example: plasticizers, lubricants, emulsifying agents, pigments, rheology additives, catalysts, flow control agents, optical brightening agents, flame retardants, antistatic agents and blowing agents.



   The co-stabilizers are added, for example, in concentrations of 0.01 to 10% relative to the total weight of the organic matter to be stabilized.



   The fillers and reinforcing agents (section 12 of the list), for example talc, calcium carbonate, mica or kaolin, are added to the polyolefin in concentrations, for example, from 0.01 to 40% by relative to the total weight of the polyolefin to be stabilized.



   The fillers and reinforcing agents (section 12 of the list), for example alkali metal hydroxides, especially aluminum hydroxide or magnesium hydroxide, are added to the polyolefin in concentrations, for example, of 0 , 01 to 60% relative to the total weight of the polyolefin to be stabilized.



   The carbon black is added as filler to the polyolefin in concentrations which are suitably from 0.01 to 5% relative to the total weight of the polyolefin to be stabilized.

  <Desc / Clms Page number 85>

 



   The glass fibers are added as a reinforcing agent to the polyolefin in concentrations which are suitably from 0.01 to 20% relative to the total weight of the polyolefin to be stabilized.



   Other preferred compositions also include other additives, in addition to components (a) to (e), in particular alkali metal salts of higher fatty acids, for example calcium stearate.



   A conventional combination recommended for the transformation of polymeric organic materials, for example polyolefins, to form corresponding molded articles, is the combination of a phenolic antioxidant with a secondary antioxidant based on an organic phosphite or phosphonite.

   However, depending on the particular material and process, many polyolefin transformers are forced to perform operations in the region of high temperatures above about 280 C. Thanks to the incorporation of a new mixture of stabilizers of processing consisting of components (b), (c), (d) and (e), which is particularly suitable for high temperature applications, in particular in the region of temperatures above 300 ° C., molded articles and industrial materials , for example based on high density polyethylene, such as pipes and their technical variants (fittings), can be produced at a higher production rate and with less rejections. Another advantage of the present mixture of stabilizers is that it can be used in very small amounts.

   This results in a reduction in the overall concentration of antioxidant compared to conventional stabilizer mixtures. Thus, the use of a low concentration of a stabilizer with a structure of benzofuran-2-one component (b)] makes it possible to reduce by around a third the overall concentration of stabilizer in polyolefins, for example, which represents simultaneously an economic advantage.



   The incorporation of components (b), (c), (d) and (e), and optionally other additives, in the material

  <Desc / Clms Page number 86>

 organic polymer is carried out by known methods, for example before or during shaping, or else by applying the mixture of dissolved or dispersed stabilizers to the organic polymeric material, with or without subsequent evaporation of the solvent. The mixture of stabilizers consisting of components (b), (c), (d) and (e), with or without other additives, can also be added to the materials to be stabilized in the form of a masterbatch which contains these components at a concentration, for example, from 2.5 to 25% by weight.



   The mixture of stabilizers consisting of components (b), (c), (d) and (e), with or without other additives, can also be added before or during the polymerization or before crosslinking.



   The mixture of stabilizers consisting of components (b), (c), (d) and (e), with or without other additives, can be incorporated into the organic material to be stabilized as such or in a form encapsulated in waxes, oils or polymers.



   The mixture of stabilizers consisting of components (b), (c), (d) and (e), with or without other additives, can also be sprayed onto the polymer to be stabilized.



  It is capable of diluting other additives (for example the conventional additives indicated above) or their fusion products, so that they can also be sprayed with these additives on the polymer to be stabilized. The addition by spraying during deactivation of the polymerization catalysts is particularly advantageous, and it is possible to carry out the spraying using, for example, the steam used for deactivation.



   In the case of polyolefins polymerized in spherical form, it may be advantageous, for example, to apply by spraying the mixture of stabilizers consisting of components (b), (c), (d) and (e), with or without others additives.



   The materials thus stabilized can be used in a wide variety of forms, for example in the form

  <Desc / Clms Page number 87>

 of films, fibers, strips, molding compositions, profiles, or as binders for coating products, in particular powder coating products, adhesives or sealants.



   The polyolefins thus stabilized can also be used in a wide variety of forms, in particular in the form of molded articles made of thick-film polyolefins which are in permanent contact with media with extractive action, for example pipes for liquids or gases, sheets, geomembranes, strips, profiles or tanks.



   Preferred thick layer polyolefin molded articles have a layer thickness of from 1 to 50 mm, in particular from 1 to 30 mm, for example from 2 to 10 mm.



   As already mentioned, the organic materials are preferably organic polymers, in particular synthetic polymers. In this context, the thermoplastics are protected in a particularly advantageous manner. It is especially important to draw attention in this context to the remarkable activity of the new mixtures of stabilizers consisting of components (b), (c), (d) and (e) as processing stabilizers (stabilizers to the heat). To this end, they are advantageously added to the polymer before or during its transformation. However, also other polymers (for example elastomers) or lubricants or hydraulic fluids can be stabilized against degradation, for example degradation caused by light or by thermo-oxidation.

   The elastomers can be chosen from the above list of possible organic materials.



   Lubricants and hydraulic fluids are for example based on mineral oils or synthetic oils, or mixtures of such oils. Lubricants are well known to the experienced practitioner and are described in the related technical literature, for example in "Schmierstoffe und verwandte produkte" by Dieter Klamann (Verlag Chemie, Weinheim, 1982), "Das Schmiemittel- Taschenbuch" by Schewe -Kobek (Dr. Alfred Hüthig-Verlag,

  <Desc / Clms Page number 88>

 Heidelberg, 1974) and in "Ullmanns Enzyklopâdie der technischen Chemie", Vol. 13, pages 85-94 (Verlag Chemie, Weinheim, 1977).



   A preferred embodiment of the present invention is therefore the use of components (b), (c), (d) and (e) as stabilizers, in particular processing stabilizers (heat stabilizers), for organic materials, especially thermoplastic polymers, against degradation caused by oxidation, heat or light.



   The present invention also relates to a mixture of stabilizers comprising (i) at least one compound with a benzofuran-2-one structure, (ii) at least one compound from the class of organic phosphites and phosphonites, (iii) at least one compound of the class of phenolic antioxidants and (iv) at least one compound of the class of hindered amines.



   Preference is also given to mixtures of stabilizers in which the weight ratio of the components (i): (ii): (iii): (iv) is between 10: 1: 1: 0.1 and 0.01: 1 : 10: 100, especially between 5: 1: 1: 0.1 and 0.01: 1: 1: 10.



   The new mixture of stabilizers consisting of components (b), (c), (d) and (e) is characterized by excellent hydrolysis stability and an advantageous effect on color, i.e. a slight change in color of the organic matter during processing.



   Organic materials which are stabilized with the components of the present invention are particularly well protected against degradation caused by light.



   The present invention also relates to a method for stabilizing an organic material against degradation caused by oxidation, heat or light, which consists in incorporating or applying to said material at least one of each of the components (b), ( c), (d) and (e).

  <Desc / Clms Page number 89>

 



   Preference is given to a process for stabilizing polyolefins which are in long-term contact with media with extractive action, in the case where the polyolefins are molded articles of thick-layered polyolefin and have a layer thickness of 1 to 50 mm, in particular from 1 to 30 mm, for example from 2 to 10 mm, which consists in incorporating or applying to said polyolefins at least one of each of the components (b), (c), (d) and (e).



   A particularly advantageous process also is a process for stabilizing molded thick-film polyolefin articles which are in long-term contact with media with extractive action, in the case where the thick-film polyolefin molded articles are pipes or geomembranes , which consists in incorporating or applying to said molded articles at least one of each of the components (b), (c), (d) and (e).



   The term "geomembranes" refers to sheets that are used, for example, in landfills and must have a lifespan of up to 300 years.



   The media with extractive action are, for example, mineral or organic materials, liquids or gases.



   Examples of gaseous mineral materials are oxygen; nitrogen; nitrogen oxides, for example NO, nitrogen oxide or NO2 sulfur oxides, for example sulfur dioxide; halogens, for example fluorine or chlorine; Brônsted acids, for example hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid or hydrocyanic acid; and bases, for example ammonia.



   Examples of gaseous organic materials are C1-C4 alkanes, for example methane, ethane, propane or butane; carbon monoxide; carbon dioxide; and phosgene.



   Examples of liquid mineral materials are water, chlorinated drinking water and aqueous saline solutions, for example a sodium chloride solution (brine) or a sodium sulfate solution; bromine;

  <Desc / Clms Page number 90>

 acid halides, for example titanium tetrachloride, thionyl chloride, nitrosyl chloride or trimethylsilyl chloride; alkaline detergents, for example an aqueous solution of sodium hydroxide (NaOH), an aqueous solution of potassium hydroxide (KOH), an aqueous solution of ammonia, an aqueous solution of sodium bicarbonate or an aqueous solution of carbonate sodium.



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



   Examples of organic solvents are aliphatic hydrocarbons, for example pentane, hexane, heptane, octane, gasoline, nonane or decane; alcohols, for example methanol, ethanol, isopropanol, butanol, pentanol, amyl alcohol, cyclohexanol, pentaerythritol, ethylene glycol, diethylene glycol, methylcellosolve, polyethylene glycol or glycerol; ketones, for example acetone, diethyl ketone, methyl ethyl ketone, diphenyl ketone or cyclohexanone; ethers, for example diethyl ether, dibutyl ether, tetrahydrofuran or dioxane; aromatic hydrocarbons, for example benzene, toluene or xylene; heterocyclic solvents, for example furan, pyridine, 2,6-lutidine or thiophene;

   dipolar aprotic solvents, for example dimethylformamide, diethylacetamide or acetonitrile; or surfactants.



   The media with extractive action within the meaning of the present invention are also mixtures and solutions, in particular mixtures, emulsions or solutions based on aqueous of liquid and gaseous organic and inorganic materials listed above.



   Extractive mediums to consider in particular are those that are important in the chemical industry or in landfills.



   A preferred embodiment of the invention is therefore also the use of a mixture of stabilizers

  <Desc / Clms Page number 91>

 consisting of components (b), (c), (d) and (e), with or without other additives, to improve the stability of polyolefins which are in long-term contact with media with extractive action.



   The preferred components (b), (c), (d) and (e) for use as stabilizers, the stabilization process and the mixture of stabilizers are the same as those described for the compositions formed with an organic material.



   The following examples illustrate the invention in more detail. The parts and percentages are expressed by weight.



  Example 1: Stabilization of polyethylene which is in long-term contact with water
Calcium stearate in an amount of 0.1% by weight and the stabilizers listed in Table 1 are added in the dry state to a polyethylene (hostalen CRP 100; PE-HD) removed directly from the reactor and the additives are incorporated into a Pappenmaier mixer (type 20) for two minutes (Examples 1a to 1c).

   TABLE 1
 EMI91.1
 
 <tb>
 <tb> Examples <SEP> Stabilizers <SEP> Quantity
 <tb> (% <SEP> in <SEP> weight)
 <tb> Irgafos # 168c) <SEP> 0, <SEP> 10
 <tb> Example <SEP> 1aa) <SEP> Irganox1010) <SEP> 0, <SEP> 10
 <tb> Chimassorb944e) <SEP> 0, <SEP> 20
 <tb> Combination <SEP> (101) <SEP> f) <SEP> 0.05
 <tb> b) <SEP> Irgafos # 168c) <SEP> 0.10
 <tb> Example <SEP> 1b <SEP> @
 <tb> Irganox # 1010d) <SEP> 0, <SEP> 05
 <tb> Chimassorb944e) <SEP> 0, <SEP> 20
 <tb> Combination <SEP> (101) <SEP> f) <SEP> 0.05
 <tb> Irgafos # 168c) <SEP> 0.10
 <tb> Example <SEP> 1cb) <SEP> Irganox # 1010d) <SEP> 0.05
 <tb> Chimassorb119g) <SEP> 0, <SEP> 20
 <tb>
 

  <Desc / Clms Page number 92>

 a) Example of comparison. b) Example according to the invention. c) Irgafosa168 (Ciba Spezialitätenchemie AG) is the
 EMI92.1
 tris (2,4-di-tert-butylphenyl) phosphite.

   d) Irganoxa1010 (Ciba Spezialitätenchemie AG) is the pentaerythritol ester of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid (compound of formula VIc). e) Chimassorba944 (Ciba Spezialitätenchemie AG) designates linear or cyclic condensation products prepared from N, N'-bis (2,2, 6, 6-tetramethyl-4-piperidyl) - hexamethylenediamine and 4-tert-octylamino -2, 6-dichloro-1,3, 5-triazine [compound of formula (H5)]. f) The combination (101) is a mixture of about 85 parts by weight of the compound of formula Va and about 15 parts by weight of the compound of formula Vb.

   g) Chimassorb # 119 (Ciba Spezialitätenchemie AG) designates condensation products prepared from 2-chloro-
4,6-di (4-n-butylamino-1,2, 2,6, 6-pentamethylpiperidyl) -
1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane [compound of formula (H6)].



     Irgafos's'168, Irganoxa1010, Chimassorba944 and Chimassorba119 are protected trademarks of Ciba Spezialitätenchemie AG.



   In a Schwabenthan extruder, the stabilized polyethylene is homogenized at 2200C and transformed into granules at 300 C. For the water extraction experiments, test sheets measuring 44 mm x 20 mm x 2 mm are pressed from the granules of the individual formulations (Examples 1a to 1c) using a bench press. To facilitate the release of the test sheets, the pressing is carried out between two aluminum sheets.



   The stabilizer extraction experiments are carried out with deionized water. The heat treatment of the extraction vessels is carried out in a convection oven from Heraeus (Hanau, Germany) with a maximum temperature difference of 1.5 C. For extraction tests

  <Desc / Clms Page number 93>

 glass containers are used below the boiling point of water. In the case of a water temperature of 105 C, stainless steel pressure-holding vessels are used. In view of the risk of oversaturation of the water by the stabilizer, the quantity of liquid for the experiments is fixed at approximately 400 ml for approximately 70 g of polymer and the water is replaced by new water at regular time intervals. , especially after each sample collection.



   The test sheets are subjected to the experimental conditions described above at 800C for 50 days.



  After the end of the extraction experiments, the content of residual stabilizer and the oxidation induction time (TIO) of the test sheets are measured.



   The residual sterically hindered phenol content, Irganox1010, is determined using an internal standard in an HPLC device of the Spectra Physics SP 8800 type with an automatic sampler and a UV / visible detector of the Spectra 200 type. Chromatography is carried out at room temperature with a column of the Hyperchrome type of 125 x 4.6 mm, packed with Nucleosil C 185 kam. The injection volume is 14 days. at a flow rate of 1.5 ml / minute. UV detection is carried out at 270 nm.



   The residual content of sterically hindered triazine amines, Chimassorb 944 and Chimassorb 119, is determined using a Lambda 15 UV spectrometer of Perkin Elmer by measuring the difference between the absorbances at 246.4 and 300 nm.



   The oxidation induction time is determined using a DuPont 910 differential scanning calorimeter from TA Instruments (Alsenau, Germany) and with a sample quantity of 5 to 10 mg, and defines the time period,
 EMI93.1
 in minutes, under constant thermal stress (190OC / C02) until complete decomposition of the polyethylene sample begins. The longer the oxidation induction time, the better the stabilization of the polyethylene and the more the polyethylene is stable with respect to the extraction water which is in long-term contact with the polyethylene.

  <Desc / Clms Page number 94>

 



   The results show that the stability of polyolefins which are in long-term contact with media with extractive action is improved when the mixture of stabilizers comprises a new component (b), (c), (d) and (e). The results are summarized in Table 2.



   TABLE 2 Maintenance in water for 50 days at 80 C
 EMI94.1
 
 <tb>
 <tb> Content
 <tb> residual <SEP> Time
 <tb> Example <SEP> Stabilizer <SEP> in <SEP> stabili- <SEP> induction
 <tb> Example <SEP> Stabilizer
 <tb> reading <SEP> after Oxidation <SEP>,
 <tb> 50 <SEP> days <SEP> minutes
 <tb> to <SEP> 80 C
 <tb> 0.10 <SEP>% <SEP> Irgafos168C)
 <tb> 1axa) <SEP> 0, <SEP> 10 <SEP>% <SEP> Irganox1010d) <SEP> 52 <SEP>% <SEP> 34
 <tb> 0.20 <SEP>% <SEP> Chimassorb # 944e) <SEP> 57 <SEP>%
 <tb> 0.05 <SEP>% <SEP> Combination <SEP> (101) <SEP> f)
 <tb> 0.10 <SEP>% <SEP> Irgafos # 168c) <SEP> 38
 <tb> 1bb) <SEP> 0.05 <SEP>% <SEP> Irganox # 1010d) <SEP> 56 <SEP>%
 <tb> 0.20 <SEP>% <SEP> Chimassorb # 944e) <SEP> 71 <SEP>%
 <tb> 0.05 <SEP>% <SEP> Combination <SEP> (101) <SEP> f)
 <tb> 0.10 <SEP>% <SEP> Irgafos # 168c)
 <tb> 1cb) <SEP> 0.05 <SEP>% <SEP> Irganox # 1010d) <SEP> 57% <SEP> 39
 <tb> 0,

  20 <SEP>% <SEP> Chimassorb119g) <SEP> 70 <SEP>%
 <tb>
 Notes a) to g), see Table 1.



  Example 2: Polypropylene stabilization in the case of multiple extrusion and at particularly high temperatures
1.5 kg of polypropylene powder (Profax # 6501), having been initially stabilized with 0.008% of Irganox # 1076 (compound of formula VIb) (having a melt index of 3.2, measured at 230 ° C. and under 2.16 kg)

  <Desc / Clms Page number 95>

 with 0.1% calcium stearate and 0.015-0.20% of the stabilizers listed in Table 3. This mixture is extruded in an extruder whose body has a diameter of 20 mm and a length of 400 mm at 100 revolutions per minute , the maximum temperature of the extruder being adjusted to 280,300, 320 and 340 C. For cooling, the extrudate is drawn through a water bath, then cut into granules. These granules are extruded several times.

   After 5 extrusions, the melt index is measured (at 2300C under 2.16 kg).



  A strong increase in the melt index indicates a significant breakdown of the chains and therefore poor stabilization. The results are summarized in Table 3. They show that the stability of the polypropylene is improved if the mixture of stabilizers contains a new component (b), (c), (d) and (e).



   TABLE 3
 EMI95.1
 
 <tb>
 <tb> Hint <SEP> from
 <tb> Quantity <SEP> fluidity
 <tb> Example <SEP> Stabilizer
 <tb> (% <SEP> in <SEP> weight) <SEP> after
 <tb> 5 <SEP> extrusions
 <tb> Irgafos # 168c) <SEP> 0, <SEP> 10
 <tb> 2a <SEP> Irganox # 1010d) <SEP> 0.10 <SEP> 17, <SEP> 5
 <tb> Chimassorb # 944e) <SEP> 0, <SEP> 20
 <tb> Combination <SEP> (101) <SEP> f) <SEP> 0.015
 <tb> Irgafos # 168c) <SEP> 0.10
 <tb> 2bb) <SEP> Irganox # 1010d) <SEP> 0.05 <SEP> 8.6
 <tb> Chimassorb # 944e) <SEP> 0, <SEP> 10
 <tb> Combination <SEP> (101) <SEP> f) <SEP> 0.015
 <tb> irgafos # 168c) <SEP> 0.10
 <tb> 2cb) <SEP> Irganox # 1010d) <SEP> 0.05 <SEP> 8.0
 <tb> Chimassorb # 119g) <SEP> 0.10
 <tb>
 Notes a) to g), see Table 1 of Example 1.


    

Claims (29)

 CLAIMS 1. Composition characterized in that it comprises a) an organic material which is sensitive to a degradation caused by oxidation, heat or light, b) at least one compound with a structure of benzofuran-2-one, c) at least one compound from the class of organic phosphites and phosphonites, d) at least one compound from the class of phenolic antioxidants, and e) at least one compound from the class of sterically hindered amines.  2. Composition according to claim 1, characterized in that it comprises, as component (b), a compound corresponding to formula I  EMI96.1  in which, if n is 1, R1 is a naphthyl, phenanthryl, anthryl group, 5.6, 7, 8-tetrahydro-2-naphthyl, 5.6, 7, 8-tetrahydro-1-naphthyl, thienyl, benzo [b] thienyl, naphtho [2, 3-b] - thienyl, thianthenyl, dibenzofuryl, chloromenyl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, iso-indolyl, indolyl, indinolinyl, quinolinyl, purinyl, quinolyl , quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, P-carbolinyl, phenanthridinyl, acridinyl, peridinyl, phenanthrolinyl, phenazinyl, isothiazolyl,  phenothiazinyl, isoxazolyl, furazanyl, biphenylyl, terphenylyl, fluorenyl or phenoxazinyl, unsubstituted or substituted by one or more C 1 -C 4 alkyl groups, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio,  <Desc / Clms Page number 97>  hydroxyl, halogen, amino, C1-C4 alkylamino, phenylamino or di (C1-C4 alkyl) amino, or R1 is a group of formula II  EMI97.1  and, if n is 2, R1 is an unsubstituted phenylene or naphthylene group  EMI97.2  or substituted by one or more C1-C4 alkyl or hydroxyl groups; or is R. -X-R-, R, R, Ret Rc are each, independently of the others, hydrogen, chlorine or a hydroxyl group, C 1 -C 6 alkyl, phenyl C 7 -C 9 alkyl;  phenyl unsubstituted or substituted by one or more C1-C4 alkyl groups; C 1-6 cycloalkyl unsubstituted or substituted by one or more C1-C4 alkyl groups; C1-C18 alkoxy, C1-C18 alkylthio, C <-C <alkylamino, di (C1-C4 alkyl) amino, C1-C25 alkanoyloxy, C1-C25 alkanoylamino, C3-C25 alkenoyloxy, alkanoyloxy C3-C25 which is interrupted by oxygen, sulfur or N-R14; C6-C9 cycloalkylcarbonyloxy, benzoyloxy or benzoyloxy substituted with one or more C1-C12 alkyl groups;  or the  EMI97.3  radicals R2 and R3 or the radicals R3 and R4 or the radicals R4 and Ru, with the carbon atoms to which they are attached, form a joined benzene nucleus, R4 can also be - (CH2) P-COR15 or - (CH2) qOH or, if R3, R5 and R6 are each hydrogen, R4 can also be a group of formula III  EMI97.4  WHERE R1 is as defined above for n = 1,  <Desc / Clms Page number 98>    EMI98.1  R6 is hydrogen or a group of formula IV  EMI98.2    EMI98.3  where R4 is not a group of formula III and R1 is as defined above for n = 1, Ry, Rg, Rq, R.  Q and R11 are each, independently of the others, hydrogen, halogen or a hydroxyl group, C1-C2 alkyl, C-Cc alkyl interrupted by oxygen, sulfur or N-R <<; C1-C6 alkoxy, C2-C25 alkoxy interrupted by oxygen, sulfur or N-R14; C <-Ce alkylthioen, C-C alkenyl, C-C alkenyloxy, C-Cpe alkynyl, C - C - alkynyloxy, Cy-Cg phenylalkyl, C7-C9 phenylalkoxy; phenyl unsubstituted or substituted by one or more C1-C4 alkyl groups; phenoxy unsubstituted or substituted by one or more C1-C4 alkyl groups; cycloalkyleenCe-Cgnon substituted or substituted by one or more C1-C4 alkyl groups; C 1-6 cycloalkoxy unsubstituted or substituted by one or more C 1-4 alkyl groups;  C1-C4 alkylamino, di (C1-C4 alkyl) amino, C-Ce alkanoyl, C C-Ce alkanoyl interrupted by oxygen, sulfur or N-R.,; C <-CE alkanoyloxy, C-CE alkanoyioxy interrupted by oxygen, sulfur or::; N-R14; C1-C2S alkanoylamino 1-14 1-C251 C-CE alkenoyl / C-C alkenoyl. interrupted by oxygen, sulfur or::;  N-R14; C-C alkenoyloxy 14 3 251 C-C alkenoyloxy interrupted by oxygen, sulfur or N-R.,; C6-Cq cycloalkylcarbonyl, C6-C9 cycloalkylcarbonyloxy; benzoyl unsubstituted or substituted by one or more C1-C12 alkyl groups; benzoyloxy unsubstituted or substituted by one or more groups  EMI98.4  ? ? ? 1 1 C1-C6 alkyl; -o-C-C-R -0-C-C-O-R, 1 15 1 1 23 "H m 19 H R22  <Desc / Clms Page number 99>  or, in formula II, the radicals R7 and Rg or the radicals Rg and Roll, with the carbon atoms to which they are attached, form a joined benzene nucleus, R12 and R13 are each, independently of the other, an unsubstituted or substituted phenylene or naphthylene group  EMI99.1  by one or more C1-C4 alkyl groups' R14 is hydrogen or a C1-C alkyl group.,  EMI99.2  RIS is a hydroxyl group, -o'-M a group / R24 alkoxy in C.-C.  g or-N 1 18 11-1 R25  EMI99.3  R16 and R17 are each, independently of the other, hydrogen, CF3, a C1-C12 alkyl group or a phenyl group, or else R16 and R17, with the carbon atom to which they are attached, form a ring of C5-C8 cycloalkylidene which is unsubstituted or substituted 1 to 3 times by a C1-C4 alkyl group, R. g and R19 are each, independently of the other, hydrogen, a C1-C4 alkyl group or a phenyl group, R20 is hydrogen or a C1-C4 alkyl group, R21 is hydrogen; an unsubstituted phenyl group  EMI99.4  or substituted by one or more C1-C4 alkyl groups; a C1-C25 alkyl group; a C-Cc alkyl group interrupted by oxygen, sulfur or # N-R14;  a C7-C9 phenylalkyl group which is unsubstituted or substituted 1 to 3 times on the phenyl moiety with a C1-C4 alkyl group; a C7-C25 phenylalkyl group which is unsubstituted or substituted 1 to 3 times on the phenyl moiety by a group  EMI99.5  C1-C4 alkyl and interrupted by oxygen, sulfur or:  NR, or the radicals Ro and R., with the atoms 21, with the carbon atoms to which they are attached, form a C5-C12 cycloalkylene ring which is unsubstituted or substituted 1 to 3 times by an alkyl group in Cl-C4, R22 is hydrogen or C1-C4 'alkyl  EMI99.6  R23 is hydrogen or a C1-C2 alkanoyl group, C-Cc alkenoyl, C3-C25 alkanoyl interrupted by oxygen, sulfur or) N-R14; C-C alkanoyl. 11 14 2 25  <Desc / Clms Page number 100>    EMI100.1  substituted with a di (C1-C6 alkyl) phosphonate group;  C 1-6 cycloalkylcarbonyl, thénoyie, furoyie, unsubstituted benzoyie or benzoyl substituted by one or more C1-Cl2 alkyl groups,  EMI100.2    EMI100.3  R24 and R25 are each, independently of the other, hydrogen or a C1-Cl alkyl group, R26 is hydrogen or a C1-C8 alkyl group 'R27 is a direct bond or a C1-C4 alkylene group -cl8, CC alkylene. interrupted by oxygen, sulfur or N-R. ; C-C alkenylene. p, 18 C-Co alkylidene, Cy-Co phenylalkylidene, C-Cg cycloalkylene, C ene bicycloalkylene or Cy-Cg bicycloalkylene, unsubstituted phenylene or phenylene substituted by one or more alkyl groups  EMI100.4  below. ; -f, or r. 0 S - 1 '' +) Rg is a hydroxyl group, -0 "" TM, a r / R24 alkoxy group in C.-C. g or-N, Ra 0 Il R29 is oxygen, -NH-or N-C-NH-R, / 30  EMI100.5  R30 is a C1-C1 alkyl group. or phenyl, R31 is hydrogen or a C1-Cl8 alkyl group, 'M is a metal cation of valence r, X is a direct bond, of, oxygen, sulfur or - NR31-,  <Desc / Clms Page number 101>  n is 1 or 2, p is 0.1 or 2, q is 1,2, 3,4, 5 or 6, r is 1,2 or 3, and s is 0.1 or 2.  3. Composition according to claim 1, characterized in that it comprises, as component (b), a compound corresponding to formula V  EMI101.1  in which R2 is hydrogen or a C1-C6 alkyl group, R3 is hydrogen, R4 is hydrogen or a C1-C6 alkyl group; Re is hydrogen,  EMI101.2  R, Rg, Rn, R. Q and R11 are each, independently of R7, R e others, hydrogen, a C1-C4 alkyl group or a C1-C4 alkoxy group. provided that at least two of the radicals R7, R8, R9, R10 and R11 are hydrogen.  4. Composition according to claim 1, characterized in that component (b) is a compound corresponding to the formula Va or Vb  EMI101.3  or a mixture of the two compounds of formulas Va and Vb.  <Desc / Clms Page number 102>    5. Composition according to claim 1, characterized in that it comprises, as component (c), a compound corresponding to formula 1, 2, 5 or 6  EMI102.1    EMI102.2  in which is the number 2 and y is the number 1, 2 or 3, A is a C2-C1S'p-phenylene or 2-Cl alkylene group, l p-phenyl 'p-biphenylene, if y 'is 1, E is a C-C6 alkyl group, -OR' or fluorine, if y is 2, E is a p-biphenylene group, if y is 3, E is N (CHCHO- )., R ', R' and R'3 are each, independently of the others, a C1-C1 alkyl group, Cy-Co phenylalkyl, cyclohexyl, phenyl or phenyl substituted by 1 to 3 alkyl groups having in total 1 with 18 carbon atoms, R, is hydrogen or a C1-C6 alkyl group, R'e is hydrogen or a methyl group,  <Desc / Clms Page number 103>    x is a direct bond, Y is oxygen,    EMI103.1  Z is a direct bond or -CH (R ') - and R "6 is a C1-C4' alkyl group. 6. Composition according to claim 1, characterized in that the component (c) is the phosphite of tris- (2,4-di-tert-butylphenyl), bis (2,4-di-tert-butyl-6-methylphenyl) and ethyl phosphite or tetrakis (2,4,4-biphenylenediphosphonite) di-tert-butylphenyl).  7. Composition according to claim 1, characterized in that it comprises, as component (d), a compound corresponding to formula VI  EMI103.2  in which R, is a C1-C4 alkyl group 'n is 1,2, 3 or 4,  EMI103.3  u Il X is a methylene group, -cHZ-CH2 "c-Y- or o 0 Il - CH-C-O-CH-CH-,  EMI103.4  Y is oxygen or-NH-; and if n is 1,  EMI103.5  0 il X est-CH-CH-C-Y-, where Y is fixed to R, and  EMI103.6  R2 is a C1-C25 alkyl group; and if n is 2,  EMI103.7  0 Il X is-CH-CH-C-Y- where y is attached to R2, and  EMI103.8  R2 is a C-C alkylene group. , C4-C12 alkylene interrupted by oxygen or sulfur; or if Y is - NH-, R can also be a direct bond;  and,  <Desc / Clms Page number 104>    EMI104.1  if n is 3, 0 II X is a methylene group or 2 C 0 CH CH o the ethylene group is attached to R2, and  EMI104.2    EMI104.3  if n is 4, 0 it X is -CH, -CHg-C-Y-, where Y is fixed to R, and  EMI104.4  R2 is a C <-C alkanetetrayl group. .  8. Composition according to claim 7, characterized in that, in the compound of formula VI, if n is 1, R2 is a C1-C2 alkyl group.  9. Composition according to claim 7, characterized in that, in the compound of formula VI, if n is 2, R2 is a C2-C8 alkylene, C4-C8 alkylene group interrupted by oxygen or sulfur; or if Y is -NH-, R2 can also be a direct bond; and, if n is 4, R2 is a C-C6 alkanetetrayl group.  10. Composition according to claim 7, characterized in that, in the compound of formula VI, R, is a methyl or tert-butyl group, n is 1,2 or 4,  EMI104.5  0 il X est-CH2cH2c-Y-,  EMI104.6  Y is oxygen or-NH-; and if n is 1, R2 is a C14-C18 alkyl group; and if n is 2, R2 is a C4-C6 alkylene group or a C4-C6 alkylene group interrupted by oxygen; and if n is 4, R2 is a C4-C6 alkanetetrayl group.  <Desc / Clms Page number 105>    11. Composition according to Claim 1, characterized in that the component (d) is at least one compound of formula VIa, VIb, VIc or VId  EMI105.1    <Desc / Clms Page number 106> 12. Composition according to claim 1, characterized in that the component (e) contains at least one group of formula XII or XIII  EMI106.1    EMI106.2  in which G is hydrogen or a methyl group, and G1 and G2 are each hydrogen, a methyl group or are together oxygen. 13. Composition according to claim 1, characterized in that the component (e) is a compound of the formulas H1, H2, H3, H4, H5, H6 and H7  EMI106.3    <Desc / Clms Page number 107>    EMI107.1  in which m is a number between 2 and 200.  <Desc / Clms Page number 108>    14. Composition according to claim 1, characterized in that it comprises, as component (a), a natural, semi-synthetic or synthetic polymer.  15. Composition according to claim 1, characterized in that it comprises, as component (a), a thermoplastic polymer.  16. Composition according to claim 1, characterized in that it comprises, as component (a), a polyolefin.  17. Composition according to claim 1, characterized in that it comprises, as component (a), polyethylene or polypropylene or one of their copolymers with mono-and diolefins.  18. Composition according to claim 1, characterized in that it comprises, as component (a), a molded article in polyolefin with a thick layer.  19. Composition according to claim 18, characterized in that the thick-layer polyolefin molded article has a layer thickness of 1 to 50 mm.  20. Composition according to claim 18, characterized in that the thick-film polyolefin molded article is a polyolefin pipe or a polyolefin geomembrane.  21. Composition according to claim 1, characterized in that it comprises, as component (a), a polyolefin which is in long-term contact with a medium with extractive action.  22. Composition according to claim 21, characterized in that the medium with extractive action is an organic or mineral, liquid or gaseous material.  23. Composition according to claim 1, characterized in that the component (b) is present in an amount of 0.0005 to 5% relative to the weight of the component (a).  24. Composition according to claim 1, characterized in that the components (c), (d) and (e) are present in an amount of 0.01 to 10% relative to the weight of the component (a).  <Desc / Clms Page number 109>    25. Composition according to claim 1, characterized in that it also comprises other additives, in addition to the components (a), (b), (c), (d) and (e).  26. Stabilizer mixture, characterized in that it comprises i) at least one compound with the structure of benzofuran-2-one, ii) at least one compound from the class of organic phosphites and phosphonites, iii) at least one compound of the class of phenolic antioxidants, and iv) at least one compound of the class of hindered amines.  27. Stabilizer mixture according to claim 26, characterized in that the weight ratio of the components (i): (ii): (iii): (iv) is between 10: 1: 1: 0.1 and 0, 01: 1: 10: 100.  28. A method for stabilizing an organic material against degradation caused by oxidation, heat or light, characterized in that it consists in incorporating or applying to said material at least one of each of the components (b), (c), (d) and (e) according to claim 1.  29. Use of a mixture of components (b), (c), (d) and (e) according to claim 1 as stabilizers for organic materials against degradation caused by oxidation, heat or light.