FR2746805A1 - STABILIZATION OF POLYAMIDES, POLYESTERS AND POLYKETONES WITH ORGANIC PHOSPHITE AND STERICALLY ENCLOSED PHENOL - Google Patents

Abstract

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 such as, for example, Irganox 1076, Irganox 1010, Irganox 245, Irganox 259, Irganox 1035, Irganox 3114 or Irganox 3125 (Ciba-Geigy), the use of these compounds for the stabilization of polyamides, polyesters or polyketones against degradation by l oxygen, heat and / or light, and a method of stabilizing these plastics.

Description

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 these latter for the stabilization of polyamides, of polyester or polyketones against the degradation due to oxidation, heat or light, as well as a method of

  stabilization of 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 symmetrical triaryl phosphite

  tris (2,4-di-tert-butylphenyl) phosphite (Irgafos 168, Ciba

  Geigy). These mixtures of known stabilizers can not meet all the requirements established for polyamides, polyesters and polyketones. These stabilizer mixtures are known to reduce the initial coloration and development of polyamide staining during oven aging, and to reduce degradation of the mechanical properties of the polyamide during oven aging and exposure to light. . As a disadvantage of these mixtures of

  stabilizers, it is often observed that these phosphites tend to come out.

  US Pat. Nos. 4,318,845 and 4,374,219 describe alkanolamine esters of cyclic phosphites of 1,1'-biphenyl-2,2'diyl and of 1,1'-alkylidene-2-biphenyl. , 2'-diyl as stabilizers for organic polymers and lubricating oils, in particular as stabilizers for the

  form for polyolefins, elastomers, polyesters and polycarbonates.

  It has now been found that well-determined phosphite-containing stabilizer mixtures, selected from US Pat. Nos. 4,318,845 and 4,374,219, and a well-defined group of 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 come out.

  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 (CH 3) 3 C z (CH 3) 3 o

J, P-P-O-CH 2 CH 2 -N (I)

(CH 3) 3 C 3) 3

C (CH3) 3

  and c) at least one compound of formula II

H3 \ C CH3

H3C " 'C_

  In which R.sub.1 represents a C.sub.1 -C.sub.4 alkyl, n.sub.2, .sub.2 or .sub.4 alkyl residue;

O O

  X is methylene, -CH-CH2-C-Y- or -CH-C-O-CH-CH2-, Y is an oxygen atom or -NH1-; and when n is 1, X is -CH2-CH2-C-Y-, Y being bonded to R2, and R2 is C1-C2s alkyl; and when n is 2, where X is the group --CH - CH 2 --CY - Y, Y being bonded to R 2, and R 2 is a C 2 -C 12 alkylene radical, C 4 -C 12 alkylene interrupted by oxygen or sulfur or, when Y is -NH1, R2 may be further a direct bond; and when n is 3, X is a methylene or -CH2-C-O-CH2-CH- residue, the ethylene group being bonded to R2, and R2 is; and, when n is 4, where X is -CH2-CH2-C-Y-, Y being attached to R2, and

  R2 is a C 1 -C 10 alkanetetrial residue.

  An alkyl radical having up to 25 carbon atoms denotes a linear or branched radical such as, for example, a methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or 2-ethylbutyl radical, n-pentyl,

  isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-

  heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-

  octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl or docosyl. A preferred meaning of R 1 is methyl or tert-butyl. Particularly preferred R 2 is C 1 -C 20 alkyl, especially C 1 -C 18 alkyl, for example C 4 -C 8 alkyl. A specially preferred meaning of

  R2 is C8-C8alkyl, especially C4-C18alkyl, for example C18alkyl.

  A C2-C12 alkylene radical denotes a linear or branched residue such as, for example, an ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene or decamethylene residue.

  dodecamethylene. A preferred meaning of R2 is, for example, C2-alkylene.

  C1o, especially C2-C8 alkylene. A particularly preferred meaning of R 2 is, for example, C 4 -C 8 alkylene, especially C 4 -C 6 alkylene, for example

the remaining hexamethylene.

  A C4-C12 alkylene radical interrupted by oxygen or sulfur can be interrupted one or more times and represents, for example, a residue

  -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 C4-C10 alkylene residue interrupted by oxygen or sulfur, in particular a C4-C8 alkylene radical interrupted by oxygen or sulfur, for example an alkylene residue in the form of C4-C6 interrupted by oxygen or sulfur. A particularly preferred meaning of R2 is -CH2CH2-O-CH2CH2-O-CH2CH2or

-CH2CH2-O-CH2CH2-.

  An alkanetetric residue of 4 to 10 carbon atoms is, for example, CH 2 1 CH (CH 2 -C) 2 (pentaerythrityl), CH 2 CH 2 CH 2 CH 2 CH 2.

  CH 2 CH 2 CH 2 CH 2, CH 2 CH 2 CH 2 CH 2 CH 2 CH 2

I I I I

  -CH-C1H2-CH-CH2-CH-CH2-CH- or -CH-CH2-CH-CH2-CH2-CH-CH2-CH2-.

  The pentaerythrityl group is preferred.

  Component (c) can also be a mixture of different phenols to

  steric hindrance of formula II.

  Useful compositions contain as component (c) at least one compound of formula II wherein when n is 1, R2 is

a C 1 -C 20 alkyl residue.

  Preferred compositions containing as component (c) at least one compound of formula II wherein, when n is 2, R2 is a C2-C8 alkylene radical, C4-C8 alkylene interrupted by oxygen or sulfur, or when Y is -NH-, R2 may be further a direct bond; and when n is 4,

  R2 represents a C4-C8 alkanetetrial residue.

  Other preferred compositions contain as component (c) at least one compound of formula II wherein R, represents a methyl or tert-butyl residue, is not equal to 1, 2 or 4, where X is - CH 2 -CH 2 -C - Y-, Y represents an oxygen atom or -NH-; and when n is 1, R 2 represents a C 1-4 alkyl radical; and when n is 2, R2 is C4-C6 alkylene or C4-C6 alkylene interrupted by oxygen; and when n is 4,

  R2 represents a C4-C6 alkanetetrial residue.

  Other compositions of interest contain as component (c) at least one compound of formula II, the compound of formula II being a compound having one of formulas IIa to IIh: HC

H3 \ CH3

  H3C C x H HO CH2-CH2-C-NH- (CH2) 3- (IIa), Irganox 1098

H; / \ C / H-CH --- (H) -

H3C

H3C 2

H3C

\ C CH3

H3

II3C 'C O

  HO> CH 2 -CH, -C-O-Co 8H37 (IDb), Irganox 1076

H3C ../

/ CH

H3C CH3

\ CH3C3 I

  HC0 il HO C CH2-CH-C-O-CH2 -C (IIc), Irganox 1010 H3C

I -CH4

  H3C H3C H CHCI_ i _OC -2COC_ (IId), Irganox 245

  HO> ,,, CH 2 CH 2 -C-O-CH 2 -CH 2 -O-CH 2 -H 3 C 2

H3C

H3C 0CH3

  HO CH 2 -CH-C - (CH 2) (He), Irganox 259

H3C- C

/ CH3

__ H3C - 2

H3CC

\ O

H3C 'C I

  H 2 2 C (II), Irganox 1035 H; CH 2 CH 2 CH (CH 2) 5 CH 3 H 3 CH 3

H3C 2

CH

HH3 CH3

o He /

  HO.O.R R3 = -H (CH (-C-O-C-CH2) SH (/ h), Irganox 1325.

H3CC

1 CCHH

1 0 HCH CHC

R H 3CH3C /

O NO

## STR5 ## wherein R 1 OH (IIg), Irganox 314.

R R CH3

O HH3C

CH3H

1 0 C

  Irganox 1098, Irganox 1076, Irganox 1010, Irganox 245, Irganox 259, Irganox 3114, Irganox 1035 and Irganox 3125 are trademarks

from the firm Ciba-Geigy.

  The compositions containing as component (c) at least one compound of formula II are preferred, the compound of formula II being a compound of formula IIa, IIb, IIc or IId, in particular a compound of formula IIa, IIb or IIc, for example

a compound of formula Hia.

  Component (b) of the composition according to the invention, the phosphite of formula I, is known and its preparation is described in US Pat. Nos. 4,318,845 and 4,374,219 cited at the beginning, in example 4. The phosphite may be in different variants, as described for example in the following US patent documents. U.S. Patent No. 5,276,076 discloses an amorphous solid form of the phosphite of Formula I. US Patent 5,334,739 discloses the crystalline form ca of the phosphite of Formula I. US Patent 5,326,802 discloses the crystalline form 3 and US Pat. No. 5,321,031, the crystalline form y of the phosphite of formula I. The phosphite of formula I is marketed

  under the trademark Irgafos 12 (Ciba-Geigy).

  Component (c) of the composition according to the invention, namely the

  compounds of formula II are known and are partly commercially available.

  Possible methods of preparation for the compounds of formula II can be found

  for example, U.S. Patent 3,330,859 or 3,960,928.

  "Polyamides" means aliphatic or aromatic polyamides or copolyamides derived from diamines and acids

  dicarboxylic acids and / or aminocarboxylic acids or corresponding 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, and polyamides. amorphous of the Trogamid PA 6-3-T and Grilamid TR 55 type.

  Such polyamides are generally known and commercially available.

  Useful compositions contain as component (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.

  The polyesters may be homopolymers or copolymers synthesized from dicarboxylic acids and diols or acids.

  aliphatic, cycloaliphatic or aromatic hydroxycarboxylic.

  The aliphatic dicarboxylic acids can contain 2 to 40 carbon atoms, the cycloaliphatic dicarboxylic acids 6 to 10 carbon atoms, the aromatic dicarboxylic acids 8 to 14 carbon atoms, the aliphatic hydroxycarboxylic acids 2 to 12 carbon atoms and the acids

  aromatic and cycloaliphatic hydroxycarboxylic 7 to 14 carbon atoms.

  The aliphatic diols can contain 2 to 12 carbon atoms, the cycloaliphatic diols 5 to 8 carbon atoms and the aromatic diols 6 to 16

carbon atoms.

  Aromatic diols are those in which two hydroxy groups are attached to a single aromatic hydrocarbon residue or to different residues

aromatic hydrocarbons.

  In addition, the polyesters may 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, 1,3,5tri (hydroxyphenyl) benzene, 2,4-dihydroxybenzoic acid or

  2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane).

  In the case of polyesters obtained from at least 2 monomers, these

  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.

  Suitable aliphatic dicarboxylic acids are those having 2 to 40 carbon atoms, for example oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, pimelic acid and adipic acid. , trimethyladipic acid, sebacic acid, azelaic acid and dimer acids (dimerization products of unsaturated aliphatic carboxylic acids such as oleic acid), alkylated malonic and succinic acids such as octadecylsuccinic acid. As cycloaliphatic dicarboxylic acids, one takes in

  1,3-cyclobutanedicarboxylic acid, 1,3cyclopentane

  dicarboxylic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, 1,3- and 1,4-

  dicarboxymethyl) cyclohexane, 4,4'-dicyclohexyldicarboxylic acid.

  Suitable aromatic dicarboxylic acids are particularly

  terephthalic acid, isophthalic acid, o-phthalic acid, and 1,3-, 1,4-, 2,6-

  or 2,7-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-acid

  diphenylsulfonedicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 1,1,3-

  trimethyl-5-carboxy-3- (p-carboxyphenyl) indane, oxy-4,4'dibenzoic acid,

  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-naphthalene

  dicarboxylic. Other suitable dicarboxylic acids are those containing -CO-NH- groups; they are described in 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 (cf. DE-A 2,121,184 and 2,533,675), mono- or bishydantoines, optionally halogenated benzimidazoles or parabanic acid. Carboxyalkyl groups

  can then contain 3 to 20 carbon atoms.

  Suitable aliphatic diols are linear or branched aliphatic glycols, especially those containing 2 to 12, in particular 2 to 6 carbon atoms.

  carbon in the molecule, for example: ethylene glycol, 1,2- and 1,3-

  propylene glycol, 1,2-, 1,3-, 2,3- or 1,4-butanediol, pentylglycol, neopentylglycol, 1,6-hexanediol, 1,12dodecanediol. A suitable cycloaliphatic diol is, for example, 1,4-dihydroxycyclohexane. Other suitable aliphatic diols are, for example, 1,4-bis (hydroxymethyl) cyclohexane, diols

  aromatics-aliphatics such as p-xylyleneglycol or 2,5-dichloro-

  xylylene glycol, 2,2-di (P3-hydroxyethoxyphenyl) propane and polyoxyalkylene

  glycols such as diethylene glycol, triethylene glycol, polyethylene glycol or polypropylene glycol. The alkylenediols are preferably linear and contain in

  particularly 2 to 4 carbon atoms.

  Preferred diols are alkylenediols, 1,4-dihydroxycyclohexane 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 bisphenols, 3-

  hydroxyalkyls, in particular 3-hydroxyethyls such as 2,2-bis [4 '- (, 3-

  hydroxyethoxy) phenyl] propane. Other bisphenols are mentioned below.

  Another group of suitable aliphatic diols is the heterocyclic diols described in German Patent Specification 1,812,003.

  2,342,432, 2,342,372 and 2,453,326. Examples are N, N'-bis (P3hydroxyethyl) -

  , 5-dimethylhydantoin, N, N'-bis (, -hydroxypropyl) -5,5-dimethylhydantoin,

  methylenebis [N- (P3-hydroxyethyl) -5-methyl-5-ethylhydantoin], methylenebis [N-

  (3-hydroxyethyl) -5,5-dimethylhydantoin], N, N'-bis (3-hydroxyethyl) benzimidazo

  lone, N, N'-bis (β3-hydroxyethyl) tetrachlorobenzimnidazolone or N, N'bis (P-

  hydroxyethyl) tétrabromobenzimidazolone. As aromatic diols, monocyclic diphenols and in particular bicyclic diphenols carrying a hydroxyl group on each aromatic ring are taken into consideration. By aromatic is preferably meant aromatic hydrocarbon radicals such as, for example, the phenylene radicals or

  naphthylene. In addition, for example, hydroquinone, resorcinol or 1,5, 2,6- and 2,7-

  dihydroxynaphthalenes, mention should be made in particular of bisphenols which can be represented by the following formulas:

R 'R' R 'R'

HO OH HO

A A

HO

R "R" R "R"

R 'R'

HO OH

A A

R "R"

R 'R'

R "R"

R R "

R 'R'

HO OH

A A

R "R"

R 'R'

A A AH

R "R"

  The hydroxyl groups may be in the meta position, but in particular in the para position, R 'and R "may represent in these formulas alkyl residues of 1 to 6 carbon atoms, halogen atoms such as chlorine or bromine, and in particular hydrogen atoms, A may be a direct bond, an oxygen or sulfur atom, -SO-, -SO2-, C = O, -P (O) (C1-C20) alkyl - , or one

  remains alkylidene, cycloalkylidene or optionally substituted alkylene.

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

trichloroethylidene.

  Examples of optionally substituted alkylene radicals are the residues

  methylene, ethylene, phenylmethylene, diphenylmethylene, metylphenylmethylene.

  Examples of cycloalkylidene residues are cyclopentylidene residues,

  cyclohexylidene, cycloheptylidene and cyclooctylidene.

  Examples of bisphenols are: bis (p-oxide or sulfide)

  hydroxyphenyl, bis (p-hydroxyphenyl) sulfone, bis (phydroxyphenyl) methane,

  bis (4-hydroxyphenyl) -2,2'-biphenyl, phenylhydroquinone, 1,2bis (p-

  hydroxyphenyl) ethane, 1-phenyl-bis (p-hydroxyphenyl) methane, diphenyl-bis (p-

  hydroxyphenyl) methane, diphenyl-bis (p-hydroxyphenyl) ethane, bis (3,5-

  dimethyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) -p-

  diisopropylbenzene, bis (3,5-dimethyl-4-hydroxyphenyl) -mdiisopropylbenzene,

  2,2-bis (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane, 1,1- or 2,2-bis (phydroxy-

  phenyl) butane, 2,2-bis (p-hydroxyphenyl) hexafluoropropane, 1,1dichloro-

  1,1,1-trichloro-2,2-bis (p-hydroxyphenyl) ethane, 1,1-bis (phydroxyphenyl) -

  cyclopentane and in particular 2,2-bis (p-hydroxyphenyl) propane (bisphenol A) and

  1,1-bis (p-hydroxyphenyl) cyclohexane (bisphenol C).

  Suitable hydroxycarboxylic acid polyesters are

  polycaprolactone, polypivalolactone or polyesters of 4-

  hydroxycyclohexanecarboxylic 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 gained the greatest importance, particularly poly (alkylene terephthalates). The molding compositions according to the invention are thus preferred in which the polyester is synthesized from at least 30 mol%, preferably at least 40 mol%, aromatic dicarboxylic acids and at least 30 mol%. mol%, preferably at least 40 mol%, of alkylenediols with preferably 2 to 12 carbon atoms,

carbon, compared to polyester.

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

and / or isophthalic acid.

  Particularly suitable polyesters are PET, PETG (glycol-modified polyethylene terephthalate) or PBT and compounds

  corresponding, PET and its copolymers being especially preferred.

  By polyketones is meant synthetic materials which are formed by polymerization of carbon monoxide with unsaturated hydrocarbons of the

  as described for example in patent documents EP-A-0 222 454 or EP-A-0 222 454.

A-0 685 517.

  Compositions as described above, in which components (b) and (c) are together in an amount of from 0.05 to 5%, in particular from 0.1 to 5%, for example from 0.1 to 2%. %, in relation to the mass of

component (a), are advantageous.

  Compositions in which the mass ratio of components (b): (c) is from 10: 1 to 1:10, in particular from 5: 1 to 1: 5,

example between 4: 1 and 1: 2.

  In addition to components (b) and (c), the compositions of the invention may contain additional additives or costabilizers, such as, for example: 1. Antioxidants

  1.1. alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-

  tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-

  4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-

  methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6dioctadecyl-4-

  methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethyl

  phenol, linear or branched nonylphenols in the side chain, such as

  for example, 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (methyl)

  yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1-yl) phenol, 2,4-dimethyl-6- (1-

  methyltridec-1-yl) phenol and mixtures thereof.

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

  butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-

  ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.

  1.3. hydroquinones and alkylated hydroquinones, for example 2,6di-tert-

  butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tertamyl-

  hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-ditert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5di-tert-butyl-4- hydroxyanisole,

  3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-) adipate

  hydroxyphenyl). 1.4. tocopherols, for example α-tocopherol, 13-tocopherol, γ-tocopherol,

  5-tocopherol and their mixtures (vitamin E).

  1.5. hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis (6-tert-butyl-4-

  methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'thiobis (6-tert-butyl-3-

  methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'thiobis (3,6-di-sec)

  amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.

  1.6. alkvlidenbisphenols, for example 2,2'-methylenebis (6-tertbutyl-4-

  methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylene

  bis [4-methyl-6- (ac-methylcyclohexyl) phenol], 2,2'-ethylenebis (4-methyl-6-

  cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-

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

  2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (a)

  methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-

  nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-

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

  2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-

  tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tertbutyl-4-hydroxy-2-

  methylphenyl) -3-n-dodecylmercaptobutane, bis [3,3-bis (3'-tertbutyl-4'-hydroxy)

  phenyl) butyrate] ethylene glycol, bis (3-tert-butyl-4-hydroxy-5-methylphenyl) -

  dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methyl) terephthalate

  benzyl) -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, 2,2bis (5-tert-butyl-

  4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5-tert-butyl)

4-hydroxy-2-methylphenyl) pentane.

  1.7. O- compounds. N- and S-benzylated e.g. 3,5,3 'oxide, 5'tetra-tert-

  butyl-4,4'-dihydroxydibenzyl, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl 4-hydroxy-3,5-di-tertbutylbenzylmercaptoacetate,

  tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl) dithioterephthalate

  3-hydroxy-2,6-dimethylbenzyl), bis (3,5-di-tert-butyl) -hydroxy-

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

  1.8. hydroxybenzyl malonates, for example 2,2-bis (3,5-di-tertbutyl-2-

  hydroxybenzyl) dioctadecyl malonate, 2- (3-tert-butyl-4-hydroxy-5-methyl-

  benzyl) dioctadecyl malonate, 2,2-bis (3,5-di-tert-butyl-4hydroxybenzyl) -

  didodecylmercaptoethyl malonate, 2,2-bis (3,5-di-tert-butyl-4hydroxy)

  benzyl) di [4- (1,1,3,3-tetramethylbutyl) phenyl] malonate].

  1.9. hydroxybenzylated aromatic compounds, for example 1,3,5-triis (3,5-di-

  tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-ditert-butyl) -4-

  hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxy-

benzyl) phenol.

  1.10. triazine compounds, for example 2,4-bis (octylmercapto) -6 (3,5-di-

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

  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-4hydroxyphenoxy) -

  1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4hydroxybenzyl) isocyanurate, 1,3,5-diisopropyl

  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-hydroxy-

  phenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxy-

benzyl) isocyanurate.

  1.11. benzylphosphonates, for example 2,5-di-tert-butyl-4-hydroxy-

  dimethyl benzylphosphonate, 3,5-di-tert-butyl-4hydroxybenzylphosphonate

  Di-tert-butyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 5-

  dioctadecyl tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt

  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-4hydroxyphenyl) -

octyl carbamate.

  1.13 esters of p- (3,5-di-tert-butyl-4hydroxyphenyl) 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, neopentyl glycol, thiodiethylene glycol, diethylene glycol,

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

  bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol,

  trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha2,6,7-

  trioxabicyclo [2.2.2] octane. 1.14. esters of "- (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, 1,9nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) -

  isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thia-

  pentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-

  phospha-2,6,7-trioxabicyclo [2.2.2] octane. 1.15. esters of 3 (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyalcohols, for example with methanol, ethanol or octanol,

  octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-

  propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol,

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

  bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol,

  trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha2,6,7-

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, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,

  trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2. 2] octane.

  1.17. amides of B- (3,5-di-tert-butyl-4hydroxyphenyl) propionic acid, by

  for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene

  diamine, N, N'-bis (3,5-di-tert-butyl-4hydroxyphenylpropionyl) trimethylene

  diamine, N, N'-bis (3,5-di-tert-butyl-4hydroxyphenylpropionyl) hydrazine, N, N'-

  bis {2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl} oxamrnide (Naugard

XL-1 from the firm Uniroyal).

  1.18. ascorbic acid (vitamin C).

  1.19. aminated antioxidants, for example N, N'-diisopropyl-pphenylenediamine,

  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-pphenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'di (naphth-2-yl) -p-phenylenediamine , the

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

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

  cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (ptoluenesulfonamido) diphenyl-

  amine, N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, a

  octylated diphenylamine, for example p, p'-di-tert-octyldiphenylamine, 4-n-

  butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-

  dodecanoylaminophenol, 4-octadecanoylaminophenol, di (4-methoxyphenyl) -

  amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenyl-

  methane, 4,4-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diamino-

  diphenylmethane, 1,2-di [(2-methylphenyl) amino] ethane, 1,2di (phenylamino) -

  propane, (o-tolyl) biguanide, di [4- (1 ', 3'-dimethylbutyl) phenyl] amine, an N-

  octylated phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tertoctyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of isopropyl /

  mono- and dialkylated isohexyldiphenylamines, a mixture of tertbutyldiphenyl-

  mono- and dialkylated amines, 2,3-dihydro-3,3-dimethyl-4H-1,4benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl / tertoctylphenothiazines, a mixture of mono- and dialkylated tertoctylphenothiazines, N-allylphenothiazine,

  N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethyl);

  piperidin-4-yl) hexamethylenediamine, bis (2,2,6,6-tetramethyl) sebacate

  piperidin-4-yl), 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethyl-

piperidin-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-5 '(1,1,3,3-

  tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2-hydroxyphenyl) -5-

  chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5chlorobenzoate

  triazole, 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 (α, α-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-chloroacetate;

  benzotriazole, 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'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) -

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

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

  triazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2isooctyloxycarbonylethyl) phenyl) -

  benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 (benzotriazole-2-)

  yl) phenol]; the trans-esterification product of 2- [3'-tert-butyl-5 '- (2-methoxy)

  carbonylethyl) -2'-hydroxyphenyl] benzotriazole with polyethylene glycol 300;

  [R-CH2CH2-COO-CH2CH2-] 2 with R = 3'-tert-butyl-4'-hydroxy-5 '- (2Hbenzotriazole)

  2-yl) phenyl; 2- [2'-hydroxy-3 '- (α, α-dimethylbenzyl) -5' - (1,1,3,3-tetramethylbutyl) -

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

  dimethylbenzyl) phenyl] benzotriazole.

  2.2. 2-hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-

  octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy and 2'-hydroxy-

  4,4'-dimethoxy. 2.3. optionally substituted benzoic acid esters, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) resorcinol,

  benzoylresorcinol, 2,4-di-tertbutyl-3,5-di-tert-butyl-4-hydroxybenzoate

  phenyl, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 3,5-ditert-butyl-4-

  octadecyl hydroxybenzoate, 2-methyl-3,5-di-tert-butyl-4-hydroxybenzoate

  4,6-di-tert-butylphenyl. 2.4. acrylates, for example ethyl-3-cyano-3,3-diphenylacrylate or

  of isooctyl, methyl-carbomethoxycinnamate, α-cyano-p-methyl-p-

  methyl or butyl methoxycinnamate, α-carbomethoxy-pmethoxycinnamate

  of methyl, N- (3-carbomethoxy-13-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, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, dithiocarbamate of

  dibutylnickel, nickel salts of monoalkyl esters of 4-hydroxy-3,5-di-

  tert-butylbenzylphosphonic acid, such as methyl or ethyl esters,

  complexes of nickel with ketoximes such as 2-hydroxy-4-methylphenyl-

  undecylketoxime, nickel complexes with 1-phenyl-4-lauroyl-5-

  hydroxypyrazole, optionally with other ligands.

  2.6. sterically hindered amines, for example bis (2,2,6,6-

  tetramethylpiperidin-4-yl), bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate,

  bis (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, bis (1- (1,1,2,6,6-pentamethylpiperidin-4-yl) sebacate,

  octyloxy-2,2,6,6-tetramethylpiperidin-4-yl), n-butyl-3,5-ditert-butyl-4-

  bis (I, 2,2,6,6-pentamethylpiperidyl) hydroxybenzylmalonate, the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear condensation products or cyclic N, N'-

  bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tertoctylamino

  2,6-dichloro-1,3,5-s-triazine, tris nitrilotriacetate (2,2,6,6-tetramethyl-4-

  piperidyl), tetrakis 1,2,6,4-butanetetracarboxylate (2,2,6,6-tetramethyl-4-

  piperidyl), 1,1 '- (1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), 4-

  benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine,

  bis (2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) 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 (1,1-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, the

  condensation product of 2-chloro-4,6-di (4-n-butylamino-2,2,6,6-tetramethyl)

  piperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, the product of

  condensation of 2-chloro-4,6-di (4-n-butylamino-1,2,2,6,6pentamethylpiperidyl)

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

  7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3dodecyl-11- (2,2,6,6-

  tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1 - (1,2,6,6,6-penta)

  methyl-4-piperidyl) pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy and 4-

  stearyloxy-2,2,6,6-tetramethylpiperidine, the condensation product of N, N'-

  bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4cyclohexyl-

  amino-2,6-dichloro-1,3,5-triazine, the condensation product of 1,2-bis (3-

  aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine, as well as 4-

  butylamino-2,2,6,6-tetramethylpiperidine (RN CAS [136504-96-6]); the 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-oxa3,8-diaza

  4-oxospiro [4,5] decane, the reaction product of 7,7,9,9-tetramethyl-2cycloundecyl-

  1-oxa-3,8-diaza-4-oxospiro [4,5] decane and epichlorohydrin, 1,1bis (1,2,2,6,6-

  pentamethyl-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-hydroxy-

  piperidine, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidinyl)] -

  siloxane, the reaction product of a maleic anhydride / chlorolefin copolymer and

  2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-

aminopiperidine.

  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'-di-tert-butyloxanilide, 2-ethoxy-2-ethyloxanilide, N 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 oxyanilides disubstituted by methoxy in o and p, and by ethoxy in 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) -4,6bis

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

  phenyl) 1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethyl)

  phenyl) -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-butyloxypropyloxy) phenyl] -4,6-bis-

  (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy) -2-

  propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4dodecyloxy]

  tridecyloxy-2-hydroxypropyloxy) -2-hydroxyphenyl] -4,6-bis (2,4diméthylphényl) -

  1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropyloxy) 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-hydroxypropyloxy) phenyl] -1,3,5triazine, the 2-

  (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2hydroxy-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, oxalic acid bis (benzylidene) dihydrazide, oxanilide, dihydrazide,

  isophthalic acid, bis (phenylhydrazide) of sebacic acid, N, N'-

  diacetyldihydrazide of adipic acid, the acid N, N'-bissalicyloyldihydrazide

  oxalic acid, the N, N'-bis-salicyloyldihydrazide of thiopropionic acid.

  4. Phosphites and phosphonites, eg triphenyl phosphite, diphenyl and alkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, phosphite

  trioctadecyl, distearylpentaerythritol diphosphite, tris (2,4-di-

  tert-butylphenyl), diisodecylpentaerythritol diphosphite, diphosphite

  bis (2,4-di-tert-butylphenyl) pentaerythritol, diphosphite bis (2,6di-tert-butyl-4-

  methylphenyl) pentaerythritol, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tertbutylphenyl) pentaerythritol diphosphite, tristearylsorbitol triphosphite, the

  Tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphonite, 6-isooctyloxy-

  2,4,8,1-tetra-tert-butyl-12H-dibenzo [d, g] -1,3,2-dioxaphosphocine, 6-fluoro

  2,4,8,10-tetra-tert-butyl-1,2-methyl-dibenzo [d, g] -1,3,2-dioxaphosphocine, methyl phosphite and bis (2,4-di-tert-butyl) 6-methylphenyl), the phosphite of ethyl and

  bis (2,4-di-tert-butyl-6-methylphenyl), the phosphite of 2-ethylhexyl and (3,3 ', 5,5'-

  tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl).

  5. Hydroxylamines, for example N, N-dibenzylhydroxylamine, N, N-

  diethylhydroxylamine, N, N-dioctylhydroxylamine, N, Ndilaurylhydroxylamine,

  N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-

  dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-

  heptadecyl-N-octadecylhydroxylamine, an N, N-dialkylhydroxylamine of amines

fat of hydrogenated tallow.

  6. Nitrones, for example N-benzyl-α-phenylnitrone, N-ethyl-α-

  methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-actundecylnitrone, N-

  tetradecyl-act-tridecylnitrone, N-hexadecyl-α-pentadecylnitrone, N-octadecyl-a-

  heptadecylnitrone, N-hexadecyl-α-heptadecylnitrone, N-octadecylca-penta

  decylnitrone, N-heptadecyl-a-heptadecylnitrone, N-octadecyl-hexadecyl-

  nitrone, nitrones derived from N, N-dialkylhydroxylamines prepared from

  of fatty amines of hydrogenated tallow.

  7. Synergic thio compounds, for example dilauryl thiodipropionate or

distearyl thiodipropionate.

  8. Compounds which destroy peroxides, for example esters of the acid [5-

  thiodipropionic, for example lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole, zinc salt of 2-mercaptobenzimidazole,

  dibutylzinc dithiocarbamate, dioctadecyl disulfide, tetrakis (f [-]

  dodecylmercapto) pentaerythritol 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, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, potassium palmitate, pyrocatecholate

  of antimony 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 sulphates, preferably of alkaline

  earth; organic compounds such as mono- or polycarboxylic acids and their salts, for example 4-tertbutylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; compounds

  polymers, 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 products

natural, synthetic fibers.

  13. Other additives, eg plasticisers, lubricants, emulsifiers, pigments, flow additives, catalysts, leveling agents, optical brighteners, flame retardants, antistatic agents,

blowing agents.

  14. Benzofuranones and indolinones, for example those described in US-A-4,325,863, US-A-4,338,244, US-A-5,175,312,

  US-A-5,216,052, US-A-5,252,643, DE-A-4,316,611, DE-A-4,316,622, DE-A-

  4316876, EP-A-0 589 839 or EP-A-0591 102, or 3- [4- (2-acetoxyethoxy) -

  phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxy)

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

  ethoxy] phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzoate

  furan-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tertbutylbenzofuran-2-

  one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one, the

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

  phenyl) -5,7-di-tert-butylbenzofurane-2-one. The costabilizers, with the exception of the benzofuranones described in point 14, are added at concentrations of, for example, between 0.01 and 10% by weight.

  relative to the total mass of the polyamide, polyester or polyketone to be stabilized.

  Other preferred compositions contain, in addition to components (a), (b) and (c), further other additives, in particular phenolic antioxidants,

* light stabilizers and / or stabilizers for shaping.

  Particularly preferred additives are phenolic antioxidants (point 1 of the list), sterically hindered amines (point 2.6 of the list), phosphites and phosphonites (point 4 of the list) and compounds which destroy the

peroxides (point 8 of the list).

  Particularly preferred additives (stabilizers) are

  also benzofuran-2-ones as described in US patent documents

  A-4,325,863, US-A-4,338,244, US-A-5,175,312, US-A-5,216,052, US-A-5,252,643,

  DE-A-4,316,611, DE-A-4,316,622, DE-A-4,316,876, EP-A-0 589 839 and EP-A-

0 591 102.

  Examples of such benzofuran-2-ones are compounds of the formula ## STR1 ## wherein R 1 'is an unsubstituted or substituted carbocyclic or heterocyclic aromatic ring system; R12 'is a hydrogen atom; R, 4 'is a hydrogen atom, an alkyl residue of 1 to 12 carbon atoms, cyclopentyl or cyclohexyl or a chlorine atom; R, 3 'has the meaning of R, 2' or R14 'or represents a remainder of formula

O O

  II - (CH2) - C-OR16 ', - (CH2) -C-N (R17') 2,

O O O O

  ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ## ## STR2 ##

O O O O

  ## STR2 ## ## STR2 ## ## STR1 ## ## STR2 ##

-CH1-S-R, 9 ', /

  O-CH 2 -S-R 19 ', --CH (C 6 H 5) - C - OR 6' or -DE, o R, 6 '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 in all 3 to 16 carbon atoms, cyclopentyl, cyclohexyl, phenyl or phenyl substituted with 1 to 3 alkyl radicals having in total not more than 18 carbon atoms; carbon; s is 0, 1 or 2; the substituents R, 7 'represent, independently of one another, a hydrogen atom, an alkyl residue of 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl substituted with 1 or 2 alkyl radicals having at most 16 carbon atoms, a residue of formula -C2H4OH, -C2H4-O-CtH21 +, or O -C2H-OC-R20 ', or together with the nitrogen atom to which they are attached form a remains piperidine or morpholine; t is a number from 1 to 18; R20 'is a hydrogen atom or an alkyl radical of 1 to 22 carbon atoms or cycloalkyl of 5 to 12 carbon atoms; A represents an alkylene radical of 2 to 22 carbon atoms optionally interrupted by nitrogen, oxygen or sulfur, Ri 8 'is a hydrogen atom or an alkyl radical of 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl substituted with 1 or 2 alkyl radicals having in all at most 16 carbon atoms, or benzyl; R 9 'represents an alkyl radical of 1 to 18 carbon atoms; D is -O-, -S-, -SO-, -SO2- or-C (R2, ') 2-; the substituents R 21 'are, independently of one another, a hydrogen atom or a C 1 -C 6 alkyl residue, the two R 2' containing together from 1 to 16 carbon atoms, or else R 21 'is a phenyl radical or a radical of formula

O O

  II - (C 1-2) -C OR 11 'or - (CH 2) -C-N (R 17') 2 o s, R, 6 'and R 17' have the meanings indicated above; E is a residue of formula R 15 t R'2

R H R '

12

  wherein R, ', R, 2' and R, 4 'have the meanings given above; and R15 'is a hydrogen atom, an alkyl radical of 1 to 20 carbon atoms, cyclopentyl or cyclohexyl, a chlorine atom or a radical of formula

O O

  II -CH2-C-OR16 'or -CH2-C-N (R17') 2, o R16 'and R17' have the meanings given above, or Ri5 'form with Rl4' a tetramethylene residue. Benzofuran-2-ones in which R13 'is a hydrogen atom, an alkyl residue of 1 to 12 carbon atoms, cyclopentyl or cyclohexyl, a chlorine atom or a residue of formula (CH2) iC-OR16 are preferred. - (CH 2) CN (R 17) 2 - or -DE; o, R16 ', R17', D and E have the meanings given above, Ri6 'representing in particular a hydrogen atom or an alkyl residue of

  1 to 18 carbon atoms, cyclopentyl or cyclohexyl.

  Benzofuran-2-ones in which R 1 'is a phenyl or phenyl residue substituted by 1 or 2 alkyl radicals having a total of at most 12 carbon atoms are further preferred; R12 'is a hydrogen atom; R14 'is a hydrogen atom or an alkyl radical of 1 to 12 carbon atoms; R, 3 'is a hydrogen atom or a

O O

  alkyl residue of 1 to 12 carbon atoms, - (CH 2) s C-OR 16 ', - (CH 2) CN (R 17') 2, or -DE, R 15 'is a hydrogen atom, an alkyl residue of 1 to 20 carbon atoms

O O

  It II -CH2-C-OR16 'or -CH-C-N (R17') 2, where R15 'forms with R14' a remainder

  tetramethylene, s, R, 6 ', R' 7 ', D and E having the meanings given at the beginning.

  Other benzofuran-2-ones of particular interest are the benzofuran-2-ones in which R13 'is a hydrogen atom, an alkyl residue of 1 to 12 carbon atoms or -D-E; R 2 'and R 14' independently of one another represent a hydrogen atom or an alkyl radical of 1 to 4 carbon atoms; and R, 5 'is an alkyl residue of 1 to 20 carbon atoms, D and E having the given meanings

in the beginning.

  Finally, benzofuran-2-ones of remarkable interest are those in which R, 3 'is an alkyl radical of 1 to 4 carbon atoms or D-E; R12 'and R4' are hydrogen atoms; and R, 5 'is an alkyl radical of 1 to 4 carbon atoms, cyclopentyl or cyclohexyl, D is the group -C (R2,') 2 and E is a radical of the formula R 15

R 'H R11' the substituents R2, 'are identical or different and represent each

  an alkyl residue of 1 to 4 carbon atoms, and R 1, ', R 12', R, 4 'and RI 5' have the meanings indicated. The amount of benzofuran-2-ones added can vary within wide limits. They may, for example, be present in the compositions according to the invention in an amount of from 0.0001 to 5, preferably from 0.001 to 2, in particular from

0.01 to 2% by weight.

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

% by mass.

  Constituents (b) and (c) can also be added before or during

  polymerization or before crosslinking.

  Constituents (b) and (c) may be incorporated in component (a) to stabilize in pure form or in encapsulated form in waxes, oils or polymers. Components (b) and (c) can also be sprayed on component (a) to be stabilized. They are able to dilute other additives (for example the aforementioned additives) or these additives in the molten state, so that they can be sprayed

  with these additives on 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,

glues or mastics.

  Constituents (b) and (c) are particularly suitable as stabilizers for shaping (heat stabilizers). To this end, we add them

  advantageously before or during the shaping of component (a).

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

  degradation by oxygen, heat or light.

  Constituents (b) and (c) are distinguished by advantageous coloring properties, that is to say that they cause a slight coloration 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 we apply on

  these materials the phosphite of formula I and at least one compound of formula II.

  The present invention also relates to a mixture of stabilizers

  containing (i) the phosphite of formula I and (ii) at least one compound of formula II.

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

  and 1: 5, for example between 4: 1 and 1: 2.

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

polyketone.

  Stabilizer mixtures consisting of components (i) and (ii) are referred to as "BC blends" ("low blending" blends). They are distinguished by excellent storage stability, low volatility and outstanding flow properties (free-flowing properties). BC mixtures shown in Table 1

are particularly preferred.

Table 1

  mixture BC constituting (i) constituting (ii) mass ratio (i): (ii) Irgafos 12 ') Irganox 1010b)) 1: 1 B Irgafos 12a) Irganox 1010b "2: 1 C Irgafos 12') Irganox 101 Ob )) 1: 2 Irgafos 12 ') Irganox 1010b ")) 4: 1 E Irgafos 12') Irganox 3114c)) 1: 1 F Irgafos 12 ') Irganox 1098d)) 1: 1 G Irgafos 12') Irganox 1098d) 1: 2H Irgafos 12 ') Irganox (1076e)) 4: 1 I Irgafos 12') Irganox 1076e)) 2: 1 a) Irgafos corresponds to the compound of formula I.

  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. The

  data in parts or percentages refer to the mass.

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

plates 2.0 mm thick.

  The specimens are aged in a circulating air oven at 140 ° C. The evolution of the aging is monitored by establishing the forced-elongation diagram at intervals of 1-3 days. The end point is the time after which the residual elongation has fallen to 50% of its initial value. The stabilization is better as the time is longer. The results are gathered in the

table 2.

  The plates are aged in a circulating air oven at 80 ° C. for 1500 hours. The yellowness index (YI) of these plates is determined according to ASTM D 1925-70. Low YI values represent low staining, and high YI values show strong staining of the sample. The stabilizer mixture is all the more active as the coloring is weak. The results are collated in Table 2.

Table 2

  time in hours to yellowing index example stabilizing a residual elongation after 1500 hours to 50% at 140 C 80 C (plates) (test pieces) 12 51.5 0.2% Irgafos 168a) lb 0.2% Irganox 1098b) 282 50.0 0.2% Irgafos 12c) lc 0.2% Irganox 1098b) 369 42.0

  a) Irgafos 168 (Ciba-Geigy) is the phosphite of tris (2,4-di-tertbutylphenyl).

  (b) Irganox 1098 (Ciba-Geigy) is N, N'-bis (3,5-di-tert-butyl-4-

  hydroxyphenylpropionyl) hexamethylenediamine (compound of formula IIa).

  HC jC3 HO CH / - CI2-I C - NH - (CH2) / - (IIa) H3CC

/ CH3

  CH 3 CH 2 CH 2 -NH (CH 2) - (11a) H 3 C C

H3C 2

  c) Irgafos 12 (Ciba-Geigy) is 2,2 ', 2 "-nitrilo [triethyl-tris (3,3', 5,5'-tetra-tert-

  butyl-l-biphenyl-2,2'-diyl) phosphite]; Chemical Abstracts RN: 80410-33-9; and represents the compound of formula I.

(CH3) 3C C (CH3) 3

o

(CH3) 3C

P-O-CH 2 CH 2 -N (I)

o

(CHC H33C

  (CH3) 3 vC C (CH3) 3 3 The results of Table 2 show that the stabilizer mixture according to the invention (Example 1c) is significantly more active than the known stabilizer mixture (Example 1b).

Claims (18)

  1. Composition containing a) a polyamide, a polyester or a polyketone sensitive to degradation by oxygen, heat or light, b) the phosphite of formula (CH3) 3C C (CH3) 3 O [OP-O-CH 2 CH 2 - N () - 0 ' (CH3) 3C C (CH3) 3   and c) at least one compound of formula II H C 3 \ 1CH 3CC - '3c ca3 - R HO --- X (II)   Wherein R 1 represents a C 1 -C 6 alkyl residue, 1, 2, 3 or 4, O O   X is methylene, -CH-CH2-C-Y- or -CH2-C-O-CH-CH2-, Y is oxygen or -NH-; and when n is 1, O X is -CH / -CH2-C-Y-, Y is attached to R2, and R2 is a C1-C25 alkyl radical; and when n is 2, X is -CH-CH 2 -CH-, Y being attached to R 2, and R 2 is C 2 -C 12 alkylene, C 4 -C 12 alkylene interrupted by oxygen or sulfur or, when Y is -NH-, R2 may be further a direct bond; and when n is 3, where X is methylene or -CH2-C-O-CH-CH2-, the ethylene group being bonded to R2, and wherein R2 is N1; and, o when n is 4, where X is -CH- CH2-C-Y-, Y being attached to R2, and   R2 is a C4-C10 alkanetetrail residue.   The composition of claim 1, comprising as component (c) at least one compound of formula II wherein when n is 1, R2 is a C1-C20 alkyl residue.   3. Composition according to claim 1, containing as component (c) at least one compound of formula II wherein, when n is 2, R2 represents a C2-C8 alkylene radical, C4-C8 alkylene interrupted by oxygen or sulfur, or when Y is -NH-, R2 may be further a direct bond; and when n is 4,   R2 represents a Ca-Cs alkanetetrial residue.   4. Composition according to claim 1, containing as component (c) at least one compound of formula II wherein R1 represents a methyl or tert-butyl residue, is not equal to 1, 2 or 4, where X is a group -CHCH2 -C - Y-, Y represents an oxygen atom or -NH-; and when n is 1, R 2 represents a C 1-4 alkyl radical; and when n is 2, R2 is C4-C6 alkylene or C4-C6 alkylene interrupted by oxygen; and when n is 4,   R2 represents a C4-C6 alkanetetrial residue.   5. The composition according to claim 1, wherein component (c) represents at least one compound of formula IIa, IIb, IIc or lid: ## STR2 ## C - NH- (CH 2) / --- b H 3 Cc / C CH 3 II 1 CHOC / NH (C 2 - (IIb) H / 3 CH3 HC HO CH-CH 2- - CO- CH- - - C (Ib) H3C -2 / CH 3   ## STR5 ## - H3C - H3C 4   H3C CH3 H3CC O (IId) HO, CH-CH-CH-CHO-O-CH H3C - 2   The composition of claim 5, wherein the component (c)   is a compound of formula IIa, IIb or IIc.   7. Composition according to claim 1, wherein the polyamide is a polyamide 6, polyamide 6.6, polyamide 11 or polyamide 12 or a copolymer thereof. The composition of claim 1, wherein the polyester is a   PET, PETG or PBT or a copolymer thereof.   The composition of claim 1, wherein the components (b) and (c) are together in an amount of 0.05 to 5% based on the weight of the constituent (a).   The composition of claim 1, wherein the ratio of   mass of the constituents (b) :( c) is between 10: 1 and 1:10.   11. Composition according to claim 1, containing other additives in more components (b) and (c).   12. Composition according to claim 11, containing as other additives phenolic antioxidants, light stabilizers and / or stabilizers for shaping.   13. Composition according to claim 11, containing as other   additive at least one compound of the benzofuran-2-ones type.   14. Use of the phosphite of formula I and 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 the implementation form.   16. A process for stabilizing a polyamide, a polyester or a polyketone against degradation by oxygen, heat and / or light, characterized in that it incorporates or applies on these materials the phosphite of formula I and at least one compound of formula II, as defined in claim 1.   17. Mixture of stabilizers containing (i) the phosphite of formula I and (ii)   at least one compound of formula II as defined in claim 1.   The stabilizer mixture according to claim 17, wherein the   mass ratio of constituents (i) :( ii) is between 10: 1 and 1:10.