BE1012429A3 - STABILIZATION POLYAMIDE, POLYESTER AND polyketones PHOSPHITE WITH ORGANIC AND PHENOL hindered. - Google Patents

Abstract

The present invention relates to compositions containing a polyamide, a polyester or a polyketone, a certain organic phosphite (Irgafos r 12, Ciba-Geigy) and a sterically hindered phenol such as, for example, Irganox r 1076, Irganox r 1010 , Irganox r 245, Irganox r 259, Irganox r 1035, Irganox r 3114 or Irganox r 3125 (Ciba-Geigy), the use of these compounds for the stabilization of polyamides, of pomyesters or polyketones against degradation by oxygen, heat and / or light, and a method for stabilizing these synthetic materials.

Description

       

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   Stabilization of polyamides, polyesters and polyketones with an organic phosphite and a sterically hindered phenol
The present invention relates to compositions containing a polyamide, a polyester or a polyketone, a certain organic phosphite (Irgafos 12, Ciba-Geigy) and a sterically hindered phenol, the use of the latter for the stabilization of polyamides, of polyester or of polyketones against degradation due to oxidation, heat or light, as well as a process for stabilizing these synthetic materials.



   It is known from US Pat. No. 4,360,617 that mixtures of stabilizers containing symmetrical triaryl phosphites and certain phenolic antioxidants are particularly suitable for the protection of certain organic materials such as, for example, polyurethane, polyacrylonitrile, polyamide 12 or polystyrene against degradation due to oxidation, heat or light. As the preferred symmetric triaryl phosphite, tris (2,4-di-tert-butylphenyl) phosphite is described (Irgafos 168, CibaGeigy).



   These mixtures of known stabilizers cannot meet all the requirements established for polyamides, polyesters and polyketones. It is known that these mixtures of stabilizers reduce the initial coloration and the development of coloration of the polyamide during aging in the oven, and that they reduce the degradation of the mechanical properties of the polyamide during aging in the oven and exposure to light. . As a disadvantage of these mixtures of stabilizers, it is often observed that these phosphites tend to swell.



   In patent documents US 4,318,845 and 4,374,219, esters of alkanolamines of cyclic phosphites of 1,1-biphenyl-2, 2'-diyl and alkylidene-1, 1'-biphenyl are described. 2, 2'-diyl as stabilizers for organic polymers and lubricating oils, in particular as shaping stabilizers for polyolefins, elastomers, polyesters and polycarbonates.



   It has now been found that mixtures of stabilizers containing a well-defined phosphite, chosen from US patent documents. 4318 845 and 4 374 219, and a well-defined group of sterically hindered phenols, are particularly suitable as stabilizers for polyamides, polyesters or polyketones. The polyamides, polyesters or polyketones thus stabilized have improved properties with regard to the degradation due to oxidation, heat and / or light. In addition, the phosphite according to the invention does not reuse.

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   The present invention therefore relates to compositions containing a) a polyamide, a polyester or a polyketone sensitive to degradation by oxygen, heat or light, b) the phosphite of formula
 EMI2.1
 and c) at least one compound of formula II
 EMI2.2
 in which R represents a C1-C4 alkyl residue, n is 1, 2,3 or 4,
 EMI2.3
 0 0 Il II X is a methylene residue, -CH-CH-C-Y-or-CH-C-0-CH-CH-, Y is an oxygen atom or-NH-; and, when n is equal to 1, 0 II X is the group -CH-CH-C-Y-, Y being linked to R and R is a C, -C alkyl radical;

   and, when n is equal to 2, 0 it X is the group -CHi-CHi-C-Y-, Y being linked to R ,, and

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R2 is a C 2 -C 12 alkylene, C 1 -C 2 alkylene group interrupted by oxygen or sulfur or, when Y is -NH-, R 2 may also be a direct bond; and, when n is equal to 3,
 EMI3.1
 u Il X is a methylene residue ou-CH-C-0-CH-CH-, the ethylene group being linked to R, and OyNyO Rest j m;

   and, N y N 0 when n is equal to 4, 0 Il X represents the group -CH-CH-C-Y-, Y being linked to R, and
 EMI3.2
 R2 is a C4-CW alkanetetrayl residue
An alkyl residue having up to 25 carbon atoms denotes a linear or branched residue such as, for example, a 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, nheptyl, isoheptyl, 1,1, 3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, 2- ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyle, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1.1, 3.3, 5.5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,

   eicosyle or docosyle. A preferred meaning of R, is methyl or tert-butyl. A particularly preferred meaning of R2 is C1-C211 alkyl, in particular C1-C18 alkyl, for example C4-Clg alkyl. An especially preferred meaning of R2 is Cg-C1g alkyl, in particular C1-C4 alkyl, for example C1g alkyl.



   A C2-C alkylene residue denotes a linear or branched residue such as, for example, an ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene or dodecamethylene residue. A preferred meaning of R2 is, for example, C2-C alkylene, in particular C2-C8 alkylene. A particularly preferred meaning of R2 is for example C4-C6 alkylene, in particular C4-C6 alkylene, for example the hexamethylene residue.



   A C4-C alkylene residue interrupted by oxygen or sulfur can be interrupted one or more times and represents, for example, a residue

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 EMI4.1
 - CH2-O-CH2CH2-O-CH2-, -CH2- (O-CH2CH2-) 20-CH2-, -CH2- (O-CH2CH2-) 30-CH2-, - CH2- (O-CH2CH2-) 40 -CH2-, -CH2CH2-O-CH2CH2-O-CH2CH2- OR -CH2CH2-S-CH2CH2-. A preferred meaning of R2 is for example a C 1 -C 4 alkylene residue interrupted by oxygen or sulfur, in particular a CC alkylene residue interrupted by oxygen or sulfur, for example a C 4 alkylene residue C6 interrupted by oxygen or sulfur. A meaning
 EMI4.2
 especially preferred of R2 is -CHCH-O-CHCH-O-CHCH -or- CH. CH.-S-CH. CH-.
 EMI4.3
 



  An alkanetetrayl residue of 4 to 10 carbon atoms is for example CH- 1 2 ll - C-CHi-- (pentaerythrityl), - CH-CH-CH-CH-, 1 CH2- 1 1 1 1 - CH-CH- CH-CH-CH -, - CHCH-CH-CH-CH-CH-, 1 1 1 1 - CH-CH-CH-CHCH-CH-CH-ou-CH-CH-CH-CH-CH-CH- CH-CH-.
 EMI4.4
 



  The pentaerythrityl group is preferred.



  Component (c) can also be a mixture of different sterically hindered phenols of formula II.



   Interesting compositions contain as component (c) at least one compound of formula II in which, when n is equal to 1, R2 represents a C1-C20 alkyl radical
Preference is given to compositions containing as constituent (c) at least one compound of formula II in which, when n is equal to 2, R2 represents a C2-Cg alkylene residue, C4-Cg alkylene interrupted by oxygen or sulfur, or, when Y is -NH-, R2 may also be a direct bond; and when n is equal to 4, R2 represents a C 4 -C 6 alkanetetrayl residue.



   Other preferred compositions contain as constituent (c) at least one compound of formula II in which R represents a methyl or tert-butyl residue, n is equal to 1, 2 or 4,
 EMI4.5
 0 Il X is a group-CH-CH-C-Y-,
 EMI4.6
 Y represents an oxygen atom or-NH-; and c

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 EMI5.1
 when n is equal to 1 R2 represents a C14-C1S alkyl residue; and when n is equal to 2, R2 represents a C4-C6 alkylene or C4-C6 alkylene residue interrupted by oxygen; and when n is equal to 4, R2 represents a C4-C6 alkanetetrayl residue.



  Other interesting compositions contain as constituent (c) at least one compound of formula II, the compound of formula II being a compound having one of the formulas IIa to IIh:
 EMI5.2
 H 3c C 3 \ ./ CH3 HO -,) - CH, -CH ë-NH- (CH,), - (lia), Irganox 1098 H 3C, C, / CHHsC HC \ Il CH3 H3ci:> - 0 He - - He (IIb), Irganox &commat; 1076 -C 'HC 3 3. CH, H 3c \ CH 3 H 3 cc 0 HO c H (IIc) IrganoxX 1010 H 3c CH3 H C 3 4

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 EMI6.1
 H3C HC \ / = \! ? (IM), Irganox245 - Il HO /, C-C-C-O-CH2C-O-C H3C 2 H3C \ "" CH3 H3ci:> - 0 - Il (IIe), Irganox &commat; 259 C CH3 HO C J. CH, Hr \ HC 3 2 HO -CH, -CH, -ë-0- (CH,), - S (nf), irganox 1035 H3c, H3C, C - C CH, R, H /! / Rt- f ON. O CH, ON R3 = -CH, - -OH (IIg), Irganox3114 "CH3 0 C H3c \ CH, R H3C" / CH3. "0, QCH3 OyNyO!! R, == - (CH,), - 0-C-CH. -OH (IIh), Irganox &commat; 3125.



  R '. 'R \ /! f \ CH, 0 H, C- 3 CH

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   Irganox 1098, Irganox 1076, Irganox 1010, Irganox 245, Irganox 259, Irganox 3114, Irganox 1035 and Irganox 3125 are registered trademarks of Ciba-Geigy.



   Preference is given to compositions containing as constituent (c) at least one compound of formula II, the compound of formula II being a compound of formula
 EMI7.1
 IIa, IIb, IIe or IId, in particular a compound of formula IIa, IIb or IIe, for example a compound of formula IIa.



   Component (b) of the composition according to the invention, the phosphite of formula I, is known and its preparation is described in patent documents US 4,318,845 and 4,374,219 cited at the start, in Example 4. This phosphite can be in different variants, as described for example in the following US patent documents. US patent document 5,276,076 describes an amorphous solid form of the phosphite of formula 1. US patent document 5,334,739 describes the crystalline form of phosphite of formula 1. US patent document 5,326,802 describes the crystalline form P and patent document US 5 321 031 the crystalline form y of the phosphite of formula I.

   The phosphite of formula 1 is marketed under the registered trademark Irgafos 12 (Ciba-Geigy).



   The constituent (c) of the composition according to the invention, namely the compounds of formula II, are known and are partly available commercially.



  Possible preparation methods for the compounds of formula II can be found, for example, in U.S. Patent Documents 3,330,859 or 3,960,928.



   "Polyamides" should be understood to mean aliphatic or aromatic polyamides or copolyamides derived from diamines and dicarboxylic acids and / or corresponding aminocarboxylic acids or lactams. Suitable polyamides are for example PA 6, PA 11, PA 12, PA 46, PA 6.6, PA 6.9, PA 6.10 or PA 6.12, PA 10.12, PA 12.12, as well as polyamides amorphous types Trogamid PA 6-3-T and Grilamid TR 55. Polyamides of this type are generally known and available commercially.



   Interesting compositions contain as constituent (a) polyamide 6, polyamide 6.6, polyamide 11 or polyamide 12 or their copolymers, in particular polyamide 6 or polyamide 6.6, or polyamide 6 modified with an elastomer or polyamide 6.6 mixed with polypropylene.



   As regards the polyesters, they may be homopolymers or copolymers synthesized from dicarboxylic acids and diols or aliphatic, cycloaliphatic or aromatic hydroxycarboxylic acids.



   Aliphatic dicarboxylic acids can contain 2 to 40 atoms

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 carbon, cycloaliphatic dicarboxylic acids 6 to 10 carbon atoms, aromatic dicarboxylic acids 8 to 14 carbon atoms, aliphatic hydroxycarboxylic acids 2 to 12 carbon atoms and aromatic and cycloaliphatic hydroxycarboxylic acids 7 to 14 carbon atoms.



   Aliphatic diols can contain 2 to 12 carbon atoms, cycloaliphatic diols 5 to 8 carbon atoms and aromatic diols 6 to 16 carbon atoms.



   The term “aromatic diols” is intended to mean those in which two hydroxy groups are linked to a single aromatic hydrocarbon residue or to different aromatic hydrocarbon residues.



   In addition, the polyesters can be crosslinked with small amounts, for example from 0.1 to 3 mol% relative to the dicarboxylic acids present, of monomers having more than two functions (for example pentaerythritol, trimellitic acid, 1,3,5-tri (hydroxyphenyl) benzene, 2,4-dihydroxybenzoic acid or le2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane).



   In the case of polyesters obtained from at least 2 monomers, these may have a statistical distribution, or they may be block copolymers.



   Suitable dicarboxylic acids are linear or branched saturated aliphatic dicarboxylic acids, aromatic dicarboxylic acids and cycloaliphatic dicarboxylic acids.



   As aliphatic dicarboxylic acids, those which have 2 to 40 carbon atoms are taken into account, for example oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, pimelic acid, adipic acid. , trimethyladipic acid, sebacic acid, azelaic acid and dimer acids (dimerization products of unsaturated aliphatic carboxylic acids like oleic acid), alkylated malonic and succinic acids like octadecyl succinic acid.



   As cycloaliphatic dicarboxylic acids, 1, 3-cyclobutanedicarboxylic acid, 1, 3-cyclopentanedicarboxylic acid, 1, 3- and 1, 4-cyclohexanedicarboxylic acid, 1, 3- and 1 are taken into consideration. 4dicarboxymethyl) cyclohexane, 4,4'-dicyclohexyldicarboxylic acid.



   Suitable aromatic dicarboxylic acids are in particular terephthalic acid, isophthalic acid, o-phthalic acid, and 1,3-, 1,4-, 2,6or 2,7-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'diphenylsulfonedicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 1,1,3-trimethyl-5-carboxy-3- (p-carboxyphenyl) indane, l '4,4'-dibenzoic acid,

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 bis (p-carboxyphenyl) methane or bis (p-carboxyphenyl) ethane.



   Aromatic dicarboxylic acids are preferred, among which, in particular, terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid.



   Other suitable dicarboxylic acids are those which contain -CO-NH- groups; they are described in patent document DE-A-2 414 349. The dicarboxylic acids which contain N-heterocyclic rings are also suitable, for example those derived from carboxyalkylated, carboxyphenylated or carboxybenzylated monoamino-s-triazinedicarboxylic acids (see patent documents DE-A 2 121 184 and 2533675), mono-or bishydantoins, optionally halogenated benzimidazoles or parabanic acid. The carboxyalkyl groups can then contain 3 to 20 carbon atoms.



   Suitable aliphatic diols are linear or branched aliphatic glycols, in particular those which contain 2 to 12, in particular 2 to 6 carbon atoms in the molecule, for example: ethylene glycol, 1, 2- and 1,3propylene glycol , 1,2-, 1, 3-, 2, 3- or 1, 4-butandiol, pentylglycol, neopentylglycol, 1,6-hexanediol, 1,12-dodecanediol. A suitable cycloaliphatic diol is, for example, 1,4-dihydroxycyclohexane.

   Other suitable aliphatic diols are, for example, 1,4-bis (hydroxymethyl) cyclohexane, aromatic-aliphatic diols such as p-xylylene glycol or 2,5-dichloro-pxylylene glycol, 2,2-di (ss-hydroxyethoxyphenyl) ) propane and polyoxyalkylene glycols such as diethylene glycol, triethylene glycol, polyethylene glycol or polypropylene glycol. The alkylene diols are preferably linear and in particular contain 2 to 4 carbon atoms.



   Preferred diols are the alkylenediols, 1,4-dihydroxycylohexane and 1,4-bis (hydroxymethyl) cyclohexane. Ethylene glycol, 1,4-butanediol and 1,2 and 1,3-propylene glycol are particularly preferred.



   Other suitable aliphatic diols are ss-hydroxyalkylated bisphenols, in particular ss-hydroxyethylated like 2,2,2-bis [4'- (ss-hydroxyethoxy) phenyl] propane. Other bisphenols are listed below.



   Another group of suitable aliphatic diols is constituted by the heterocyclic diols described in German patent documents 1 812 003,
 EMI9.1
 2,342,432, 2,342,372 and 2,453,326. Examples are N, N'-bis (p-hydroxyethyl) - 5,5-dimethylhydantoin, N, N'-bis (p-hydroxypropyl) - 5,5 -dimethylhydantoin, methylenebis [N- (p-hydroxyethyl) -5-methyl-5-ethylHydantoin], methylenebis [N- (p-hydroxyethyl) -5, 5-dimethyl! hydantoin], laN, N'-bis (p-hydroxyethyl) benzimidazo-

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 EMI10.1
 lone, N, N'-bis (ss-hydroxyethyl) tetrachlorobenzimidazolone or N, N'-bis (p-hydroxyethyl) tetrabromobenzimidazolone.



   As aromatic diols, consideration is given to monocyclic diphenols and in particular to bicyclic diphenols carrying a hydroxyl group on each aromatic ring. The term “aromatic” preferably means aromatic hydrocarbon residues such as, for example, phenylene or naphthylene residues. In addition to, for example, hydroquinone, resorcinol or 1,5-, 2, 6- and 2,7dihydroxynaphthalenes, bisphenols which may be represented by the following formulas should be mentioned in particular:
 EMI10.2
 

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The hydroxyl groups can be in the meta position, but in particular in the para position, R ′ and R ″ can represent in these formulas alkyl radicals of 1 to 6 carbon atoms, halogen atoms such as chlorine or
 EMI11.1
 bromine, and in particular hydrogen atoms.

   A can be a direct link, a
 EMI11.2
 oxygen or sulfur atom, -SO-, -S02 - '\ C = O, -P (O) (C 1 -C alkyl: o) - or an optionally substituted alkylidene, cycloalkylidene or alkylene residue .



   Examples of optionally substituted alkylidene radicals are the ethylidene, 1, 1- or 2,2-propylidene, 2,2-butylidene, 1,1-isobutylidene, pentylidene, hexylidene, heptylidene, octylidene, dichloroethylidene, trichloroethylidene radicals.



   Examples of optionally substituted alkylene residues are the methylene, ethylene, phenylmethylene, diphenylmethylene, metylphenylmethylene radicals.



  Examples of cycloalkylidene residues are the cyclopentylidene, cyclohexylidene, cycloheptylidene and cyclooctylidene residues.



   Examples of bisphenols are: bis (p-) oxide or sulfide
 EMI11.3
 hydroxyphenyl, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, bis (4-hydroxyphenyl) -2, 2'-biphenyl, phenylhydroquinone, 1,2-bis (phydroxyphenyl) ethane, 1-phenyl-bis (p-hydroxyphenyl) methane, diphenyl-bis (p-hydroxyphenyl) methane, diphenyl-bis (p-hydroxyphenyl) ethane, bis (3,5-dimethyl 1-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) -pdiisopropylbenzene, bis (3,5-dimethyl-4-hydroxyphenyl) -m-diisopropylbenzene, 2,2-bis (3 ', 5'-dimethyl-4 '-hydroxyphenyl) propane, 1, 1- or 2,2-bis (p-hydroxyphenyl) butane, 2,2-bis (p-hydroxyphenyl) hexafluoropropane, 1, 1-dichloro- or 1,1, 1-trichloro-2,2-bis (p-hydroxyphenyl) ethane, 1,

     1-bis (p-hydroxyphenyl) cyclopentane and in particular 2,2-bis (p-hydroxyphenyl) propane (bisphenol A) and 1,1-bis (p-hydroxyphenyl) cyclohexane (bisphenol C).



   Suitable polyesters of hydroxycarboxylic acids are, for example, polycaprolactone, polypivalolactone or polyesters of 4hydroxycyclohexanecarboxylic acid or 4-hydroxybenzoic acid.



   In addition, polymers which essentially contain ester bonds, but which may also contain other bonds, for example polyesteramides or polyesterimides, are also suitable.



   Polyesters containing aromatic dicarboxylic acids have acquired the greatest importance, in particular poly (alkylene terephthalates). Preference is therefore given to the molding compositions according to the invention in which the polyester

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 is synthesized from at least 30 mol%, preferably at least 40 mol%, of aromatic dicarboxylic acids and from at least 30 mol%, preferably at least 40 mol%, of alkylenediols with preferably 2 to 12 carbon atoms, relative to the polyester.



   In particular, in this case, the alkylenediol is linear and contains from 2 to 6 carbon atoms such as, for example, ethylene glycol, the tri-, tetra- or hexamethylene glycol and the aromatic dicarboxylic acid is terephthalic acid and / or isophthalic acid.



   Particularly suitable polyesters are PET, PETG (poly (ethylene terephthalate) modified by a glycol) or PBT and corresponding compounds, PET and its copolymers being especially preferred.



   By polyketones is meant synthetic materials which are formed by polymerization of carbon monoxide with unsaturated hydrocarbons as described for example in patent documents EP-A-0 222 454 or EP-A-0685517.



   Compositions as described above, in which the constituents (b) and (c) are present together in an amount of 0.05 to 5%, in particular from 0.1 to 5%, for example from 0.1 to 2 %, relative to the mass of the constituent (a), are advantageous.



   Also preferred are the compositions in which the mass ratio of the constituents (b): (c) is between 10: 1 and 1: 10, in particular between 5: 1 and 1: 5, for example between 4: 1 and 1 : 2.



   In addition to components (b) and (c), the compositions according to the invention can contain additional additives or costabilizers, such as, for example, the following: 1. Antioxidants 1.1. alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-
 EMI12.1
 4-n-butylphenol, 2, 6-di-tert-butyl-4-isobutylphenol, 2, 6-dicyclopentyl-4methylphenol, 2- (a-methylcyc1ohexyl) -4, 6-dimethylphenol, 2, 6- dioctadecyl-4methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols in the side chain such as, for example, 2,6-dinonyl -4-methylphenol, 2,4-dimethyl-6- (I'-methylundéc-I'- yl) phenol, 2,

     4-dimethyl-6- (1'-methylheptadéc-l'-yl) phenol, 2,4-dimethyl-6- (1'-
 EMI12.2
 methyltridec-1'-yl) phenol and mixtures thereof.



  1. 2. alkylthiomethylphenols. for example 2,4-dioctylthiomethyl-6-tert-

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 butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.



  1.3. alkylated hydroquinones and hydroquinones, for example 2,6-di-tertbutyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl -4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3 stearate , 5-di-tert-butyl-4-hydroxyphenyl, bis (3,5-di-tert-butyl-4hydroxyphenyl) adipate.



  1.4. tocopherols, for example a-tocopherol, ss-tocopherol, y-tocopherol, 8-tocopherol and their mixtures (vitamin E).



  1.5. hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis (6-tert-butyl-4methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl- 3methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-secamylphenol), 4,4'-bis disulfide (2 , 6-dimethyl-4-hydroxyphenyl).



  1.6. alkylidenebisphenols, for example 2,2'-methylenebis (6-tert-butyl-4methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4 -methyl-6- (a-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2 ' methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol) , 2, 2'-methylenebis [6- (a-methylbenzyl) -4-nonylphenol], 2, 2'-methylenebis 6- (a, a-dimethylbenzyl) -4- nonylphenol], 4,4'- methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6tert-butyl-2-methylphenol), l, l-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 (5tert-butyl-4-hydroxy-2-methylphenyl) butane , 1,1-bis (5-tert-butyl-4-hydroxy-2methylphenyl) -3-n-dodecylmercaptobutane, bis [3, 3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrates d ethylene glycol, bis (3-tert-butyl-4-hydroxy-5-methylphenyl) - dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl) terephthalate -6-tert-butyl-4-methylphenyl], 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4- hydroxyphenyl) propane, 2,2-bis (5-tert-butyl- 4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5-tert-butyl- 4 -hydroxy-2-methylphenyl) p entane.



  1.7. 0- compounds. N- and S-benzylated, for example 3,5,3 ', 5'-tetra-tertbutyl-4,4'-dihydroxydibenzyl, 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, 4 -3,5-di-tert-butylbenzylmercapto-tridecyl acetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl) dithioterephthalate

  <Desc / Clms Page number 14>

 3-hydroxy-2,6-dimethylbenzyl), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
 EMI14.1
 



  1. 8. hydroxybenzylated malonates, for example 2, 2-bis (3,5-di-tert-butyl-2hydroxybenzyl) dioctadecyl malonate, 2- (3-tert-butyl-4-hydroxy-5-methyl - dioctadecyl benzyl) malonate, 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) didodecylmercaptoethyl malonate, 2,2-bis (3,5-di-tert-butyl-4 dihydroxy-benzyl) malonate 4- (1, 1, 3,3-tetramethylbutyl) phenyl].



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



  1.10. triazine compounds, for example 2,4-bis (octylmercapto) -6- (3,5-ditert-butyl-4-hydroxyanilino) -1, 3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-
 EMI14.2
 butyl-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, le 1, 3, 5-tris (3, 5-di-tert-butyl- 4-hydroxybenzyl) isocyanurate, 1, 3, 5tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) isocyanurate, 2, 4, 6-tris (3, 5-di-tertbutyl-4- hydroxyphenylethyl) -1, 3, 5-triazine, 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3 , 5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.



  1.11. benzy! phosphonates. for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate dioctadecyl, dioctadecyl 5tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.



  1.12. acylaminophenols, for example 4-hydroxyanilide of lauric acid, 4-hydroxyanilide of stearic acid, 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-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6,7trioxabicyclo [2. 2.2] octane.

  <Desc / Clms Page number 15>

 



   1.14. esters of p-5-tert-butyl-4-hydroxy-3-methylphenylpropionic acid with mono or polyalcohols, for example with methanol, ethanol, noctanol, 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-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-lphospha-2,6,7-trioxabicyclo [2. 2.2] octane.



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



  1.16. esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono or polyalcohols, for example with methanol, ethanol, octanol, 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-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
 EMI15.1
 trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6, 7-trioxabicyclo [2. 2.2] octane. 1. 17. P-f3 acid amides. 5-di-tert-butyI-4-hydroxyphenyDpropionique.

   for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, N, N'-bis {2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl ) propionyloxy] ethyl} oxamide (Naugard # XL-1 from the firm Uniroyal).
 EMI15.2
 



  1. 18. ascorbic acid (vitamin C). that (vitamin C). 1.19. amino antioxidants, for example N, N'-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p - phenylenediamine, N, N'-bis (l-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'bis (l-methylheptyl) -p-phenylenedi amine, N, N'-dicyc1ohexyl-p -phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di (napht-2-yl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N - (1, 3-dimethylbutyl) -N'-phenyl-p-

  <Desc / Clms Page number 16>

 phenylenediamine, N- (1-methylheptyl)

  -N'-phenyl-p-phenylenediamine, Ncyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfonamido) diphenylamine, N, N'-dimethyl-N, N'-di-sec-butyl -p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -l-naphthylamine, N-phenyl-2-naphthylamine , an octylated diphenylamine, for example p, p'-di-tert-octyldiphenylamine, 4-nbutylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4dodecanoylaminophenol, 4-octadecanoylaminophenol, di (4-amyl) , 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,

  4'-diaminodiphenylmethane, 1,2-di [(2-methylphenyl) amino] ethane, 1,2-di (phenylamino) propane, (o-tolyl) biguanide, di [4- (1 ', 3'-dimethylbutyl) phenyl] amine, an octylated N-phenyl-1-naphthylamine, a mixture of mono-and dialkylated tert-butyl / tert-octyldiphenylamines, a mixture of mono-and dialkylated nonyldiphenylamines, a mixture of mono-and dialkylated dodecyldiphenylamines dialkylated, a mixture of mono and dialkylated isopropyl / isohexyldiphenylamines, a mixture of mono and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3, 3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixture of tert-butyl / tert-octylphenothiazines mono- and dialkylated,
 EMI16.1
 a mixture of mono-and dialkylated tert-octylphenothiazines,

   N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2, 2, 6, 6-tetramethyl-piperidine-4-yl ) hexamethylenediamine, bis (2,2,6,6-tetramethylpiperidine-4-yl) sebacate, 2,2,6,6-tetramethylpiperidine-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'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-S'- (1, 1,3, 3tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5- chlorobenzotriazole, 2- (3'-tert-butyl-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'-di -tert-amyl-2'-hydroxyphenyl) - benzotriazole, 2- (3 ', 5'-bis (a, a-dimethylbenzyl) -2'-hydroxyphenyl)

     benzotriazole, the
 EMI16.2
 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) -

  <Desc / Clms Page number 17>

 
 EMI17.1
 phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5'- [2- ( 2-ethylhexyloxy) carbonylethyl] -2 hydroxyphenyl) benzotriazole, te 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy- 5'- (2-isooctyloxycarbonylethyl) phenyl) - benzotriazole, 2, 2'-methylenebis [4- (1,1, 3,

     3-tetramethylbutyl) -6- (benzotriazole-2-yl) phenol]; the transesterification product of 2- [3'-tert-butyl-5'- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO-CH2CH2-] 2 with R = 3'-tert-butyl-4'-hydroxy-5 '- (2H-benzotriazole-2-yl) phenyl; 2- [2'-hydroxy-3'- (a, a-dimethylbenzyl) -5'- (1, 1, 3, 3-tetramethylbutyl) - phenyl] benzotriazole; 2- [2'-hydroxy-3'- (1, 1, 3, 3-tetramethylbutyl) -5'- (a, a- dimethylbenzyl) phenyl] benzotriazole.



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



  2.3. esters of optionally substituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 3 2,4-di-tert-butylphenyl, 5-di-tert-butyl-4-hydroxybenzoate, 3,5-di-tert-butyl-4-hydroxybenzoate, 3,5-di-tert- octadecyl butyl-4hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
 EMI17.2
 



  2. 4. acrylates, for example ethyl or isooctyl α-cyano-p, p-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-p-methyl-pmethoxycinnamate or butyl, methyl a-carbomethoxy-p-methoxycinnamate, N- (ss-carbomethoxy-ss-cyanovinyl) -2-methylindoline.



  2.5. nickel compounds, for example nickel complexes with 2,2'-thiobis [4- (1, 1, 3,3-tetramethylbutyl) phenol], such as the 1: 1 complex or the 1: 2 complex, with optionally additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, dibutylnickel dithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3,5-ditert-butylbenzylphosphonic acid, such as esters methyl or ethyl, nickel complexes with ketoximes such as 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes with 1-phenyl-4-lauroyl-5-hydroxypyrazole, possibly with other ligands.



  2.6. sterically hindered amines, for example bis (2,2,6,6tetramethylpiperidine-4-yl) sebacate, bis (2,2, 6,6-tetramethylpiperidine-4-yl) succinate,

  <Desc / Clms Page number 18>

 
 EMI18.1
 bis sebaçate (1, 2, 2, 6, 6-pentamethylpiperidine-4-yl), bis sebaçate (loctyloxy-2, 2, 6, 6-tetramethylpiperidine-4-y le), n-butyl- 3, 5-di-tert-butyl-4-hydroxybenzylmalonate bis (1,2,2,6,6-pentamethylpiperidyl), the condensation product of 2-hydroxyethyl-2,6, 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-s-triazine, tris nitrilotriacetate (2,2,6,6-tetramethyl-4piperidyl),

   tetrakis 1,2,3,6,4-butanetetracarboxylate (2,2,6,6-tetramethyl-4-
 EMI18.2
 piperidyle), l, l'- (1, 2-ethanediyl) -bis (3, 3, 5, 5-tetramethylpiperazinone), 4benzoyl-2, 2, 6, 6-tetramethylpiperidine, 4-stearyloxy-2, 2, 6, 6-tetramethylpiperidine, 2-n-butyl-2- (2-hydroxy-3, 5-di-tert-butylbenzyl) bis malonate (1, 2, 2, 6, 6-pentamethylpiperidyl), 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-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,6, 2,6, 6-tetramethylpiperidyl) succinate, linear or cyclic condensation products of N, N'-bis (2,2, 6,6-tetramethyl-4piperidyl) hexamethylenediamine and 4-morpholino-2, 6-dichloro-1,3,5-triazine, the product.

   condensation of 2-chloro-4, 6-di (4-n-butylamino-2, 2,6, 6-tetramethyl-piperidyl) -l, 3,5-triazine and 1,2-bis (3- aminopropylamino) ethane, the condensation product of 2-chloro-4, 6-di (4-n-butylamino-1, 2,2, 6, 6-pentamethylpiperidyl) - 1, 3, 5-triazine and l, 2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-
 EMI18.3
 7, 7, 9, 9-tetramethyl-1,3,8-triazaspiro [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) pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy and 4stearyloxy-2,2, 6, 6-tetramethylpiperidine, the condensation product of N, N'bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2, 6-dichloro-1,3,5-triazine, the condensation product of 1,2-bis (3aminopropylamino) ethane and 2,4,6-trichlor-1,3,5-triazine, as well as 4butylamino-2,2,6,6-tetramethylpiperidine (RN CAS [136504-96-6]);

   N- (2,2,6,6tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6,6-pentamethyl-4-
 EMI18.4
 piperidyl) -n-dodecylsuccinimide, 2-undecyl-7, 7, 9, 9-tetramethyl-l-oxa-3, 8-diaza- 4-oxospiro [4, 5] decane, the reaction product of 7, 7 , 9, 9-tetramethyl-2-cycloundecyl-1-oxa-3, 8-diaza-4-oxospiro [4, 5] decane and epichlorohydrin, l, l-bis (l, 2, 2, 6 , 6pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethylene, N, N'-bis-formyl-N, N'-bis (2,2, 6, 6-tetramethyl-4-piperidyl) hexamethylenediamine, the 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 -piperidinyl)

  ] -

  <Desc / Clms Page number 19>

 
 EMI19.1
 siloxane, the reaction product of a maleic anhydride / a-olefin copolymer and 2, 2, 6, 6-tetramethyl-4-aminopiperidine or 1, 2, 2, 6, 6-pentamethyl-4aminopiperidine.



  2. 7. diamides of oxalic acid, for example 4, 4'-dioctyloxyoxanilide, 2, 2'-diethoxyoxanilide, 2,2'-dioctyloxy-5, 5'-di-tert-butyloxanilide, 2,2'-didodecyloxy- 5,5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert -butyl-2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide, mixtures of oxanilides disubstituted by methoxy at o and p, and by ethoxy at o and P.



  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) -!, 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) -
 EMI19.2
 1, 3, 5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxy-propyloxy) phenyl] -4, 6-bis- (2, 4dimethylphenyl) -1, 3, 5- triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 2- [4 -dodecyloxy / tridecyloxy-2-hydroxypropyloxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) - 1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy -3-dodecyloxy-propyloxy) phenyl] -4,6- bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) -4,6-diphenyl- 1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butyloxy-2-hydroxy-propyloxy) phenyl] -1, 3, 5-triazine, 2- (2-hydroxyphenyl)

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



  3. Metal deactivators, for example N, N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5 -ditert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2,4-triazole, bis (benzylidene) dihydrazide of oxalic acid, oxanilide, dihydrazide of isophthalic acid, bis (phenylhydrazide) of sebacic acid, N, N'diacetyldihydrazide of adipic acid, N, N'-bis-salicyloyldihydrazide of oxalic acid, N, N'-bis-salicyloyldihydrazide of thiopropionic acid .



  4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl and alkyl phosphites, phenyl and dialkyl phosphites,

  <Desc / Clms Page number 20>

 tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris (2,4-ditert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2,4- diphosphite) di-tert-butylphenyl) pentaerythritol, bis (2,6-di-tert-butyl-4methylphenyl) pentaerythritol, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl diphosphite) ) pentaerythritol, bis (2,4, 6-tri-tert-butylphenyl) diphosphite pentaerythritol, tristearylsorbol triphosphite, tetrakis (2, 4,4'-biphenylenediphosphonite)

  4-di-tert-butylphenyl), 6-isooctyloxy- 2,4, 8, 10-tetra-tert-butyl-12H-dibenzo [d, g] -l, 3,2-dioxaphosphocine, 6-fluoro- 2,4, 8, 10-tetra-tert-butyl-12-methyldibenzo [d, g] -1, 3, 2-dioxaphosphocine, methyl phosphite and bis (2,4-di-tert-butyl-6 -methylphenyl), ethyl and bis (2,4-di-tert-butyl-6-methylphenyl) phosphite, 2-ethylhexyl phosphite and (3,3 ', 5,5' - tetra-tert- butyl-1, 1'-biphenyl-2, 2'-diyl).



  5. Hydroxylamines, for example N, N-dibenzylhydroxylarnine, N, Ndiethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, Nheptadecyl-N-octadecylhydroxylamine, an N, N-dialkylhydroxylamine of hydrogenated tallow fatty amines.



  6. Nitrones, for example N-benzyl-a-phenylnitrone, N-ethyl-a-methylnitrone, N-octyl-a-heptylnitrone, N-Iauryl-a-undecylnitrone, Ntetradecyl-a-tridecylnitrone, N-hexadecyl-a-pentadecylnitrone, N-octadecyl-a-
 EMI20.1
 heptadecylnitrone, N-hexadecyl-a-heptadecylnitrone, N-octadecyl-a-pentadecylnitrone, N-heptadecyl-a-heptadecylnitrone, N-octadecyl-a-hexadecylnitrone, nitrones derived from N, hydroxyl-dialkines hydrogenated tallow fatty amines.



  7. Thio synergistic compounds, for example dilauryl thiodipropionate or distearyl thiodipropionate.



  8. Compounds which destroy peroxides, for example esters of thiodipropionic acid, for example lauryl, stearyl, myristylic or tridecyl esters, mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole, dibutylzinc dithiocarbamate, disulfide of dioctadecyl, pentaerythritol tetrakis (ss-dodecylmercapto) propionate.



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



  10. Basic costabilizers, for example melamine, polyvinylpyrrolidone,

  <Desc / Clms Page number 21>

 
 EMI21.1
 dicyandiamid, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate.



  11. Nucleating agents, for example inorganic 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, for example ionic copolymers ("ionomers").



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



  13. Other additives, for example plasticizers, lubricants, emulsifiers, pigments, fluidity additives, catalysts, leveling agents, optical brighteners, flame retardants, antistatic agents, blowing agents.



  14. Benzofuranones and indolinones, for example those described in patent documents US-A-4,325,863, US-A-4,338,244, US-A-5,175,312, US-A-5,216,052 , US-A-5 252 643, DE-A-4316611, DE-A-4316622, DE-A- 4316876, EP-A-0589839 or EP-A-0591102, or 3- [4- (2-acetoxyethoxy ) - phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3, 3'-bis [5, 7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5, 7-di-tert-butyl- 3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3, 5-dimethylphenyl) -5, 7 -di-tert-butylbenzofuran-2- one,

   3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one,
 EMI21.2
 3- (3,4-dimethylphenyl) -5,7-di-tert -butylbenzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one.



   Costabilizers are added, with the exception of the benzofuranones described in point 14, at concentrations of, for example, between 0.01 and 10% relative to the total mass of the polyamide, polyester or polyketone to be stabilized.

  <Desc / Clms Page number 22>

 



   Other preferred compositions contain, in addition to components (a), (b) and (c), still other additives, in particular phenolic antioxidants, light stabilizers and / or shaping stabilizers .



   Particularly preferred additives are phenolic antioxidants (item 1 on the list), sterically hindered amines (item 2.6 on the list), phosphites and phosphonites (item 4 on the list) and peroxide-destroying compounds (item 8 on the list).



   Particularly preferred additional additives (stabilizers) are also benzofuran-2-ones as described in US patent documents.
 EMI22.1
 A-4 325 863, US-A-4 338 244, US-A-5 175 312, US-A-5 216 052, US-A-5 252 643, DE-A-4 316 611, DE-A- 4 316 622, DE-A-4 316 876, EP-A-0 589 839 and EP-A-0591 102.



   Examples of such benzofuran-2-ones are compounds of the formula
 EMI22.2
 wherein RI 'represents an unsubstituted or substituted aromatic carbocyclic or heterocyclic ring system; R12 'is a hydrogen atom; Rest a hydrogen atom, an alkyl residue of 1 to 12 carbon atoms,
 EMI22.3
 cyclopentyl or cyclohexyl or a chlorine atom;

   R'a the meaning of R'ou R'ou represents a remainder of formula
 EMI22.4
 0 0 Il Il - (CH,) C-OR ,, -, - (CH,) CN (R,, OOOO 0 0 0 0 - (CH-C-0-A-0-C- (CH-E, - (CH-C-NR'-A-NR'-C- (CH) -E, OO o Il 0 .-- 0 - (CHC-NR, '-A-0-C- (CHE, - (CH -CN NC- (CH-E, 2 s 18 2 s'2 s "--- 1 2 s 'Il - CH, -SR, -CH (C) -C-OR,' ou-DE, where

  <Desc / Clms Page number 23>

   R ,, 'represents a hydrogen atom or an alkyl residue of 1 to 18 carbon atoms, alkyl of 2 to 18 carbon atoms interrupted by oxygen or sulfur, dialkylaminoalkyl having a total of 3 to 16 carbon atoms , cyclopentyl, cyclohexyl, phenyl or phenyl substituted with 1 to 3 alkyl radicals having a maximum of 18 carbon atoms; s is 0.1 or 2;

   the substituents R, y're represent, independently of one another, a hydrogen atom, an alkyl residue of 1 to 18 carbon atoms, cyclopentyl,
 EMI23.1
 cyclohexyl, phenyl, phenyl substituted by 1 or 2 alkyl radicals having at most 16 carbon atoms, a radical of formula -COH, -CH-O-CtHt + i or
 EMI23.2
 u - C2H4-0-C-R ,, ', or they form together, with the nitrogen atom to which they 4 () -C-P'201'0 are linked, a piperidine or morpholine residue; t is a number from 1 to 18; R2o is a hydrogen atom or an alkyl residue of 1 to 22 carbon atoms or cycloalkyl of 5 to 12 carbon atoms;

   A represents an alkylene residue of 2 to 22 carbon atoms optionally interrupted by nitrogen, oxygen or sulfur, Rest a hydrogen atom or an alkyl residue of 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl substituted by 1 or 2 alkyl radicals having at most 16 carbon atoms, or benzyl;
 EMI23.3
 R19 represents an alkyl residue of 1 to 18 carbon atoms; D is -O -, - S -, - SO -, - SO:, - or-C (R;, /);, -; the substituents R21 'are, independently of one another, a hydrogen atom or a C 1 -C alkyl radical, the two R,' containing together from 1 to 16 carbon atoms, or else R 21 is a residue phenyl or a residue of formula
 EMI23.4
 0 0 il il - (CH,) C-OR or- (CH,) C-N (R), where s, R'6 'and RJ7' have the meanings indicated above;

   E is a remainder of formula
 EMI23.5
 

  <Desc / Clms Page number 24>

 
 EMI24.1
 in which R, /, R 'and R' have the meanings indicated above; and R 'is a hydrogen atom, an alkyl residue of 1 to 20 carbon atoms, cyclopentyl or cyclohexyl, a chlorine atom or a residue of formula
 EMI24.2
 0 0 il il - CH-C-OR, 'ou-CH-C-N (R), where R'and R, 7' have the meanings
 EMI24.3
 above, or Ris'fonte with Run remains tetramethylene.



  Benzofuran-2-ones are preferred in which R is a hydrogen atom, an alkyl residue of 1 to 12 carbon atoms, cyclopentyl or
 EMI24.4
 u il cyclohexyle, a chlorine atom or a residue of formula- (CH) gC-OR ', 0 Il - (CH2) gCN (R, ou-DE; where s, R', R ', D and E have the meanings given
 EMI24.5
 above, R'representing in particular a hydrogen atom or an alkyl residue of 1 to 18 carbon atoms, cyclopentyl or cyclohexyl.



   Furthermore, the benzofuran-2-ones are preferred in which R 1 'is a phenyl or phenyl radical substituted by 1 or 2 alkyl radicals having at most 12 carbon atoms; R12 'is a hydrogen atom; R14 'is a hydrogen atom or an alkyl residue of 1 to 12 carbon atoms; R, / is a hydrogen atom or a
 EMI24.6
 u 0 there 0 remains alkyl of 1 to 12 carbon atoms, (CH-C-OR ', - (CHJ-CN (R.') ou-DE, R,; 'is a hydrogen atom, an alkyl residue from 1 to 20 carbon atoms 0 0 il il - CH-C-OR'ou-CH-CN (R,, or R'forme with Run remains
 EMI24.7
 tetramethylene, s, R ', R', D and E having the meanings given at the beginning.



  Other particularly interesting benzofuran-2-ones are the benzofuran-2-ones in which R is a hydrogen atom, an alkyl residue of 1 to 12 carbon atoms or-D-E; R12 'and R14' independently of one another represent a hydrogen atom or an alkyl residue of 1 to 4 carbon atoms; and R,; ' is an alkyl residue of 1 to 20 carbon atoms, D and E having the meanings given at the beginning.



   Finally, remarkably interesting benzofuran-2-ones are those in which R13 'is an alkyl residue of 1 to 4 carbon atoms or-D-E; R12 'and R14' are hydrogen atoms; and RI is an alkyl residue of 1 to 4 carbon atoms, cyclopentyl or cyclohexyl, D is the group-C (R% - and E is a residue of formula

  <Desc / Clms Page number 25>

 
 EMI25.1
 the substituents R 'are identical or different and each represents an alkyl residue of 1 to 4 carbon atoms, and R ,,, Razz R] / and R' have the meanings indicated.



   The amount of benzofuran-2-ones added can vary within wide limits. They may for example be contained in the compositions according to the invention in an amount of 0.001 to 5, preferably from 0.001 to 2, in particular from 0.01 to 2% by mass.



   The incorporation of constituents (b) and (c) and possibly other additives in constituent (a) (polyamide, polyester or polyketone) is carried out according to known methods, for example before or during shaping or else by applying the constituents (b) and (c) in the form of a solution or dispersion on the constituent (a), with optionally subsequent evaporation of the solvent. One can also add to the material to be stabilized constituent (a)] the constituents (b) and (c) in the form of a masterbatch which contains them for example at a concentration of 2.5 to 25% by mass.



   Components (b) and (c) can also be added before or during the polymerization or before crosslinking.



   It is possible to incorporate into the constituent (a) to stabilize the constituents (b) and (c) in pure form or in form encapsulated in waxes, oils or polymers.



   One can also spray the components (b) and (c) on the component (a) to be stabilized. They are able to dilute other additives (for example the aforementioned common additives) or these additives in the molten state, so that they can be sprayed with these additives on the component (a) to be stabilized.



   Spray addition is particularly advantageous during the deactivation of the polymerization catalysts, which makes it possible for example to use for spraying the steam used for deactivation.



   The polyamides, polyesters and polyketones thus stabilized can be used in the most diverse forms, for example in the form of sheets, fibers, strips, molded products, profiles or binders for paints,

  <Desc / Clms Page number 26>

 glues or sealants.



   Components (b) and (c) are particularly suitable as formatting stabilizers (heat stabilizers). To this end, they are advantageously added before or during the shaping of the constituent (a).



   A preferred embodiment of the present invention is therefore the use of the phosphite of formula 1 and at least one compound of formula II as stabilizers, in particular as shaping stabilizers (thermal stabilizers) for polyamides, polyesters or polyketones against degradation by oxygen, heat or light.



   Constituents (b) and (c) are distinguished by advantageous coloring properties, that is to say that they cause a weak coloring of the polyamides, polyesters and polyketones during shaping.



   The present invention also relates to a process for stabilizing a polyamide, a polyester or a polyketone against degradation due to oxygen, heat or light, characterized in that it incorporates or phosphite of formula 1 and at least one compound of formula II are applied to these materials.



   The present invention also relates to a mixture of stabilizers containing (i) the phosphite of formula 1 and (ii) at least one compound of formula II.



   Mixtures of stabilizers are also preferred in which the mass ratio of the constituents (i): (ii) is between 10: 1 and 1: 10, in particular between 5: 1 and 1: 5, for example between 4: 1 and 1: 2.



   The preferred compounds of formula II for use as stabilizers, the stabilization process and the mixture of stabilizers are the same as those described for the compositions with a polyamide, a polyester or a polyketone.



   The mixtures of stabilizers constituted by the constituents (i) and (ii) are called "BC mixtures" ("low coloration mixtures"). They are distinguished by excellent storage stability, low volatility and remarkable flow properties (free flow properties). The BC mixtures shown in Table 1 are particularly preferred.

  <Desc / Clms Page number 27>

 



  Table 1
 EMI27.1
 
 <tb>
 <tb> mix <SEP> BC <SEP> constituent <SEP> (i) <SEP> constituent <SEP> (ii) <SEP> report <SEP> in <SEP> mass <SEP> (i) <SEP>: <SEP> (ii)
 <tb> A <SEP> Irgafos @ <SEP> 12a) <SEP> Irganox @ <SEP> 1010b)) <SEP> 1: 1
 <tb> B <SEP> Irgafos <SEP> 12a) <SEP> Irganox @ <SEP> 1010b)) <SEP> 2: 1
 <tb> C <SEP> Irgafos <SEP> 12a) <SEP> Irganox @ <SEP> 1010b)) <SEP> 1: 2
 <tb> D <SEP> Irgafos <SEP> 12a) <SEP> Irganox @ <SEP> 1010b)) <SEP> 4: 1
 <tb> E <SEP> Irganfos @ <SEP> 12a) <SEP> Irganox @ <SEP> 3114c)) <SEP> 1: 1
 <tb> F <SEP> Irgafoso <SEP> 12a) <SEP> Irganox <SEP> 1098d)) <SEP> 1 <SEP>: <SEP> 1
 <tb> G <SEP> Irgafos @ <SEP> 12a) <SEP> Irganox # <SEP> 1098d)) <SEP> 1: 2
 <tb> H <SEP> Irgafos @ <SEP> 12a) <SEP> Irganox <SEP> 1076e)) <SEP> 4 <SEP>: <SEP> 1
 <tb> 1 <SEP> Irgafos <SEP> 12a) <SEP> Irganox <SEP> 1076e)) <SEP> 2 <SEP>:

    <SEP> 1
 <tb>
 a) Irgasfos # corresponds to the compound of formula 1. b) Irganox 1010 corresponding to the compound of formula IIc. c) Irganox # 3114 corresponds to the compound of formula IIg. d) Irganox # 1098 corresponds to the compound of formula IIa. e) Irganox # 1076 corresponds to the compound of formula IIb.



   The following examples explain the invention in more detail. Data in parts or in percentages refer to mass.



  EXAMPLE 1 Stabilization of Polyamide 6
 EMI27.2
 100 parts of non-stabilized polyamide 6 granule (Ultramid B3, firm BASF) are sprayed by cryogenic micronization, and the stabilizers indicated in Table 2 are added thereto. The mixture is homogenized for 2 minutes in a Henschel mixer. The powder thus obtained is then dried at 80 ° C. for 6 hours, then it is extruded in an extruder (Berstorff type) at a maximum temperature of 240 ° C., and it is granulated. In an injection molding installation, the granulated product thus injected is injected at a maximum temperature of 240 ° C. to form dumbbell-shaped test pieces 1.0 mm thick and plates 2.0 mm thick.



   The test pieces are aged in an air circulation oven at 140 C. The evolution of aging is monitored by establishing the force-elongation diagram at intervals of 1-3 days. The time after which the residual elongation has fallen to 50% of its initial value is defined as the end point. Stabilization is all the better the longer the time. The results are collated in Table 2.



   The plates are aged in an air circulation oven at 80 ° C. for

  <Desc / Clms Page number 28>

 1500 hours. The yellowing index (YI) of these plates is determined according to standard ASTM D 1925-70. Low YI values represent weak coloration, and high YI values represent strong coloration of the sample. The mixture of stabilizers is all the more active as the coloration is weak. The results are collated in Table 2.



   Table 2
 EMI28.1
 
 <tb>
 <tb> time <SEP> in <SEP> hours <SEP> up to <SEP> index <SEP> from <SEP> yellowing
 <tb> example <SEP> stabilizer <SEP> a <SEP> elongation <SEP> residual <SEP> after <SEP> 1500 <SEP> hours <SEP> to
 <tb> of <SEP> 50 <SEP>% <SEP> to <SEP> 140 C <SEP> 80 C <SEP> (plates)
 <tb> (test pieces)
 <tb> the <SEP> 12 <SEP> 51, <SEP> 5
 <tb> 0, <SEP> 2 <SEP>% <SEP> Irgafos <SEP> 1683) <SEP> 282 <SEP> 50, <SEP> 0
 <tb> 0, <SEP> 2 <SEP>% <SEP> Irganox <SEP> 1098b) <SEP> 282 <SEP> 50.0
 <tb> 0, <SEP> 2 <SEP>% <SEP> Irgafos # <SEP> 12c)
 <tb> 1c <SEP> 0, <SEP> 2 <SEP>% <SEP> Irganox <SEP> 1098b) <SEP> 369 <SEP> 42.0
 <tb>
 
 EMI28.2
 a) Irgafos 168 (Ciba-Geigy) is tris (2,4-di-tert-butylphenyl) phosphite. b) Irganox 1098 (Ciba-Geigy) is N, N'-bis (3,5-di-tert-butyl-4hydroxyphenylpropionyl) hexamethylenediamine (compound of formula IIa).

   
 EMI28.3
 
 EMI28.4
 c) Irgafos 12 (Ciba-Geigy) is 2, 2 ', 2 "-nitrilo [triethyl-tris (3, 3', 5, 5'-tetra-tert-butyl-l, 1'-biphenyl- 2, 2'-diyl) phosphite; RN from Chemical Abstracts: 80410-33-9; and represents the compound of formula I.

  <Desc / Clms Page number 29>

 
 EMI29.1
 



   It appears from the results in Table 2 that the mixture of stabilizers according to the invention (example le) is clearly more active than the known mixture of stabilizers (example lob).


    

Claims (18)

 CLAIMS 1. Composition containing a) a polyamide, a polyester or a polyketone sensitive to degradation by oxygen, heat or light, b) the phosphite of formula  EMI30.1  and c) at least one compound of formula II  EMI30.2  in which R represents a C1-C4 alkyl residue, n is 1,2, 3 or 4,  EMI30.3  0 0 Il Il X is a methylene residue, -CH-CH-C-Y-or-CH-C-O-CH-CH-, Y is an oxygen atom or-NH-; and, when n is equal to 1,  EMI30.4  0 il X is the group -CH-CH-C-Y-, Y being linked to R2, and  EMI30.5  R2 is a C1-C2S alkyl residue;  and, when n is equal to 2,  <Desc / Clms Page number 31>    EMI31.1  0 il X is the group -CHi - CHi-C-Y-, Y being linked to R., and  EMI31.2  R is a C1-C6 alkylene radical C-C alkylene interrupted by oxygen or sulfur or, when Y is-NH-, R may also be a direct bond; and, when n is equal to 3,  EMI31.3  0 Il X is a methylene residue or-CH-C-0-CH2-CH-, the ethylene group being linked to R; ,, and zozo Rest-M '\ j; and, N y N / '1 (' "0 when n is equal to 4, 0 il X represents the group -CHi - CHI-C-Y-, Y being linked to R2, and  EMI31.4  R is a C4-ClO alkanetetrayl residue 2. Composition according to claim 1, containing as constituent (c) at least one compound of formula II in which, when n is equal to 1, R2 represents a C1-C20 alkyl residue.  3. Composition according to claim 1, containing as constituent (c) at least one compound of formula II in which, when n is equal to 2, R:, represents an alkylene residue in C-Cg, alkylene in C4-Cs interrupted by oxygen or sulfur, or, when Y is -NH-, R2 may also be a direct bond; and when n is equal to 4, R represents a C4-C8 alkanetetrayl residue.  4. Composition according to claim 1, containing as constituent (c) at least one compound of formula II in which  EMI31.5  R represents a methyl or tert-butyl residue, n is equal to 1, 2 or 4,  EMI31.6  u Il X is a group-CH-CH-C-Y-,  EMI31.7  Y represents an oxygen atom or-NH-; and when n is equal to 1  <Desc / Clms Page number 32>  R2 represents a C 4-CI 8 alkyl residue; and when n is equal to 2, R2 represents a C4-C6 alkylene or C4-C6 alkylene residue interrupted by oxygen; and when n is equal to 4, R2 represents a C4-C6 alkanetetrayl residue.  5. Composition according to claim 1, in which the constituent (c) represents at least one compound of formula IIa, IIb, IIc or IId:  EMI32.1    <Desc / Clms Page number 33> 6. Composition according to claim 5, in which the constituent (c) is a compound of formula IIa, IIb or IIc.  7. Composition according to claim 1, in which the polyamide is a polyamide 6, polyamide 6.6, polyamide 11 or polyamide 12 or one of their copolymers.  8. Composition according to claim 1, in which the polyester is a PET, PETG or PBT or one of their copolymers.  9. Composition according to claim 1, in which the constituents (b) and (c) are together in an amount of 0.05 to 5% relative to the mass of the constituent (a).  10. Composition according to claim 1, in which the mass ratio of the constituents (b): (c) is between 10: 1 and 1: 10.  11. Composition according to claim 1, containing other additives in addition to constituents (b) and (c).  12. Composition according to claim 11, containing as other additives phenolic antioxidants, light stabilizers and / or shaping stabilizers.  13. Composition according to claim 11, containing as other additive at least one compound of the type of benzofuran-2-ones.  14. Use of the phosphite of formula I and of at least one compound of formula II, as defined in claim 1, as stabilizers for polyamides, polyesters or polyketones against degradation by oxygen, heat and / or light.  15. Use according to claim 14 as stabilizers for shaping.  16. Method for stabilizing a polyamide, a polyester or a polyketone against degradation by oxygen, heat and / or light, characterized in that one incorporates therein or in that one applies on these materials the phosphite of formula 1 and at least one compound of formula II, as defined in claim 1.  17. Mixture of stabilizers containing (i) the phosphite of formula 1 and (ii) at least one compound of formula II, as defined in claim 1.  18. Stabilizer mixture according to claim 17, in which the mass ratio of the constituents (i): (ii) is between 10: 1 and 1: 10.