NL1005669C2 - Stabilization for polyamides, polyesters and polyketones. - Google Patents

Description

Stabilization of polyamides, polyesters and polycarbonates

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, for their use for stabilizing a polyamide, polyester or polyketone against oxidative, thermal and / or light-induced degradation, as well as a method of stabilizing these plastics.

It is known from US patent 4360617 that stabilizer mixtures containing symmetrical triaryl phosphites and certain phenolic antioxidants are extremely suitable for protecting certain organic materials, such as, for example, polyurethane, polyacrylonitrile, polyamide-12 or polystyrene, against oxidative, thermal or 15 protect light-induced breakdown. As a preferred symmetrical triarylphosphite bicycle, tris (2,4-di-tert-butylphenyl) phosphite (Irgafo®® 168, Ciba-Geigy) is described.

These known stabilizer mixtures cannot meet all requirements in polyamides, polyesters and polyketones. It is known that such stabilizer blends reduce the initial color as well as the color development of the polyamide during oven aging and reduce the deterioration of the mechanical properties of the polyamide during oven aging and exposure. As a drawback of these stabilizer mixtures, it is often observed that these phosphites tend to sweat.

U.S. Patent Nos. 4318845 and 4374219 disclose alkanolamine esters of cyclic 1,1'-biphenyl-2,2'-diyl- and alkyl-idene-1,1'-biphenyl-2,2'-diylphosphites as stabilizers for organic polymers and lubricating oils, in particular as processing stabilizers for polyolefins, elastomers, polyesters and polycarbonates. ------

It has now been found that a stabilizer mixture containing a particular phosphite selected from U.S. Patent Nos. 4318845 and 4374219 along with a particular group of sterically hindered phenols is extremely suitable as a stabilizer for polyamides, polyesters or polyketones. The polyamides, polyesters or polyketones thus stabilized exhibit improved oxidative, thermal and / or light-induced degradation properties. Thereby, the phosphite according to the invention is not sweated out.

The present invention therefore relates to compositions comprising a) an oxidative, thermal or light-induced degradation subject to polyamide, polyester or polyketone,

b) the phosphite of the formula I.

(CH3) 3C C (CH3) a 10

F ~ o- ch2ch2 - N

(CH 3) 3C - ^ \ J \ C (CH3) 3

L

15 and

c) at least one compound of the formula II

Γ H3C Ί 20 \ CH3 H3C \ (II) x — Rz R1 J n 25 where

R 1 represents C 1 -C 4 alkyl, η represents 1, 2, 3 or 4, 30 0 0

II II

X represents methylene, -CH2-CH2-C-Y- or -CH2-C-O-CH2-CH2-, Y is oxygen or -NH-; and when η is 1, 35 represents X -CH 2 -CH 2 -C-Y-, wherein Y is attached to R 2 and R 2 is C 1 -C 2 -alkyl; and if n is 2, 10 0 5 6 6 9 3 0

II

X represents -CH 2 -CH 2 -C-Y- wherein Y is attached to R 2 and R 2 is C 2 -C 12 alkylene, C 1 -C 12 alkylene interrupted by oxygen or sulfur; Or if Y represents -NH-, R2 additionally represents a direct bond; and if n is 3, 0

II

X represents methylene or -CH2-C-O-CH2-CH2-, wherein the ethylene group is attached to R2 and

OyNy ° R2 1 | is; and 15 o if n is k, 0 20 || X represents -CH2-CH2-C-Y- wherein Y is attached to R2 and R2 represents Cft-C10 alkane tetrayl.

Alkyl of up to 25 carbon atoms means a branched or unbranched group, such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl , 1,3 "dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3_tetramethylbutyl, 1-methylheptyl, 3" methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3 ~ trimethylhexyl, 1,1,3,3 "tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl or docosyl A preferred meaning of R 1 is methyl and tert-butyl A particularly preferred meaning of R 2 is C 1 -C 12 alkyl, especially C 1 -C 12 alkyl, eg C 1 -C 18 alkyl, A meaning of R 2 particularly preferred is C8 -C18 alkyl, especially Cl1 -C18 alkyl, eg Cl8 alkyl.

C 2 -C 12 alkylene means a branched or unbranched group, such as, for example, ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene or dodecemethylene. A preferred meaning of R2 is, for example, C2-C10al-40-kylene, especially C2-C8alkylene. A particularly preferred meaning of R2 is, for example, C 1 -C 8 alkylene, in particular C 1 -C 8 alkylene, e.g. hexamethylene.

CA-C12 alkylene interrupted by oxygen or sulfur may be single or multiple interrupted and means, for example, 5 -CH2-0-CH2CH2-0-CH2-, -CH2- (0-CH2CH2-) 20-CH2-, -ch2- (o -ch2ch2-) 3o-ch2-, -CH2- (O-CH2CH2-) - O-CHi, -ch2ch2-o-ch2ch2-o-ch2ch2- or -ch2ch2-s-ch2ch2-.

A preferred meaning of R 2 is C 1 -C 10 alkylene interrupted by oxygen or sulfur, especially C 4 -C 10 alkylene interrupted by oxygen or sulfur, e.g. 10 C 1 -C 12 alkylene interrupted by oxygen or sulfur. A particularly preferred meaning of R2 is -CH2CH2-0-CH2CH2-0-CH2CH2- or -CH2CH2-S-CH2CH2-.

For example, alkane tetrayl with k to 10 carbon atoms means CH2-

I II II

15 -CH2-C-CH2- (pentaerythrityl), -CH2-CH-CH-CH2-, -CH2-CH2-CH-CH-CH2-, ch2-

II II

-ch2-ch2-ch-ch-ch2 -ch2-, -ch2-ch2-ch-ch2-ch-ch2 -ch2- or

20 | I

-CH2-CH2-CH-CH2-CH2-CH-CH2-CH2-. Pentaerythrityl is preferred.

Component (c) can also be mixtures of various sterically hindered phenols of the formula II.

Of interest are compositions containing as component (c) at least 25 a compound of the formula I, wherein, when η is 1, R 2 represents C 1 -C 20 alkyl.

Compositions containing as component (c) at least one compound of the formula II, wherein when n is 2, R 2 is C 2 -C 8 alkylene, C 1 -C 8 alkylene interrupted by oxygen or sulfur; or, when Y represents -NH-, R2 additionally represents a direct bond; and when n is 4, R 2 represents O-Cg alkane tetrayl, 35 are preferred.

Also preferred are compositions which contain as component (c) at least one compound of the formula II, wherein R represents methyl or tert-butyl, meaning η 1, 2 or 4, 10 0 5 6 6 9 5

O

X represents -CH2-CH2-C-Y-, Y represents oxygen or -NH-; and 5 when η is 1 represents R-Cl 2 C-S; alkyl; and when n is 2, R 2 represents C 4 -C 6 alkylene or oxygen-interrupted C 1 -C 6 alkylene; and 10 when n is 4, R 2 represents C 1 -C 6 alkane tetrayl.

Also of interest are compositions containing as component (c) at least one compound of the formula I, the compound of the formula I being a compound of the formula Ha to 15 l

H, C

CH3 H cA 0

3) = x II

20 H 2 CH 2 CH 2 C NH (CH 2) 3 (Ha), Irganox® 1098 h 3 C · c; / CH, L H3C J 2

25 H3C

\ ^ ch3

hcA O

3 K ii HO-d -CH2-CH2-C-O-C1BH37 (11b), Irganox * 1076/30 Ach3 h3c 35 <f>. n s 6 5 9 th V υ '* -' 6

HX

3 / CH3 H C-C °

HaC> = X II

H0 V V CH 'CHz C 0 CHz c (lie), lrganoxe1010 H3C-cC ^ / CH3 L H3C 3 J 4

HX

3 \ / CH3 n3C / cx o / = \ II (member), Irganoxs245 HO — X 0 CH - CH —C-O — CH —CH — 0 —CH2--

HX

L J 2

HX

\ / CH3 nxV if H0_CH - CH - C - 0- (CH2) 3 (Me) t | rganox®259 H3C-C ^ / ch3 L H3C 3 J 2

HX

3 \ / CH3 H'C "Vx \\

HO - (\ /) CH - CH - C — O - (CH2) 2 S

χ_ / J 2 z (Ilf), Irganox 1035 HX ^ / c \ / CH3 L h3c 3 J 2

10 0 5 6 6 S

7 μι C CH3 RH: jC / 5 Vy ° / = (> II r3 = —CH2 - /) - OH (11g), Irganox 3114 <N '-; NX ........ M.ch3 o 3 H3C CH3 10 II p CHg

Rj Hs% / o ^ N- ^ o || r = (CHs 15 I I R3 = - (CH2) 2-0-C-CH2- (v A — OH (11h), Irganox 3125 <Νγ% M / ch3

0 A

H3C means CH3 20.

Irganok® 1098, Irganok® 1076, Irganok® 1010, Irganoj® 245, Irganox® 259, Irganox® 3114, Irganoj® 1035 and Irgano ^ 3125 are protected trade names of Ciba-Geigy.

Compositions containing as component (c) at least one compound of the formula I, wherein the compound of the formula I is a compound of the formula Ha, Ilb, IIc or lid, in particular a compound of the formula Ha , Ilb or IIc, e.g. a compound of the formula Ha are preferred.

Component (b) of the composition according to the invention, resp.

the phosphite of the formula I is known and its preparation is described in Example 4, U.S. Patent Nos. 4318845 and 4374219, cited above. This phosphite can exist in various modifications, which are described, for example, in the following US patents. U.S. Patent 5,276,776 describes a solid amorphous form of the phosphite of the formula I. U.S. Patent 5,334,739 describes the a-crystalline form of the phosphite of the formula I. In the 100 5 6 69 8

U.S. Patent 5326,802 describes the β-crystalline form, and U.S. Patent 5321031 describes the γ-crystalline form of the phosphite of the formula I. The phosphite of the formula I is commercially available under the protected name Irgafo® 12 (Ciba-Geigy) 5.

Component (c) of the composition according to the invention, respectively. the compounds of the formula II are known and partly commercially available. Possible preparation methods for the compounds of the formula II can be found, for example, in U.S. Patents 3,330,859 or 3,960,928.

By polyamides is meant aliphatic and aromatic polyamides or copolyamides, which are derived from diamines and dicarboxylic acids and / or from amino carboxylic acids or the respective lactams thereof. Suitable polyamides are for example: PA-6, PA-11, PA-12, ΡΑ-4,6, 15 PA-6,6, PA-6,9, PA-6,10 or PA-6,12, PA- 10,12, PA-12,12 as well as amorphous polyamides of the type trogamide PA 6-3-T and grilamide TR 55 · polyamides of the mentioned kind are generally known and commercially available.

Of interest are compositions comprising as component (a) polyamide-20 6, polyamide-6,6, polyamide-11 or polyamide-12 or copolymers thereof, in particular polyamide-6 or polyamide-6,6, respectively. elastomer-modified polyamide-6 or polyamide-6.6 mixed with polypropylene.

Polyesters can be homo or mixed polyesters, which are composed of aliphatic, cycloaliphatic or aromatic dicarboxylic acids and diols or hydroxycarboxylic acids.

The aliphatic dicarboxylic acids can have 2 to 10 C atoms, the cycloaliphatic dicarboxylic acids 6 to 10 C atoms, the aromatic dicarboxylic acids 8 to 14 C atoms, the aliphatic hydroxycarboxylic acids 2 to 12 C-30 atoms and the aromatic as well as cycloaliphatic hydroxycarboxylic acids 7 to 19 Contain C atoms,

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

Aromatic diols are those in which two hydroxyl groups are attached to one or different aromatic hydrocarbon groups.

Furthermore, it is possible that the polyesters in small amounts, e.g. f) S 6 6 9 e.g. 0.1 to 3 mol%, based on the dicarboxylic acids present, differential monomers (eg pentaerythritol, trimellitic acid, 1,3,5 "tri- (hydroxyphenyl) benzene, 2,4-dihydroxybenzoic acid or 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane) are branched.

Polyesters of at least 2 monomers can be statistically distributed or block copolymers.

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

Suitable aliphatic dicarboxylic acids are dicarboxylic acids with 2 to 40 carbon atoms, e.g. oxalic acid, malonic acid, dimethyl malonic acid, succinic acid, pimelic acid, adipic acid, trimethyl adipic acid, sebacic acid, azelaic acid and dimer acids (dimerization products of unsaturated aliphatic carboxylic acids such as oleic acid), alkylated malonic and succinic acid such as octadecyl succinic acid.

Suitable cycloaliphatic dicarboxylic acids are: 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3 "and 1,4-cyclohexanedicarboxylic acid, 1,3" and 1,4- (dicarbozylmethyl) cyclohexane, 4,4'-dicyclohexyl dicarboxylic acid .

Suitable suitable aromatic dicarboxylic acids are: in particular terephthalic acid, isophthalic acid, o-phthalic acid, as well as 1,3-, 1,4-, 2,6- or 2,7-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4 , 4'-diphenylsulfone dicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, 1,1,3-trimethyl-5-carboxyl-3 ”(p-carbozylphenyl} indane, 4,4'-diphenyl ether dicarboxylic acid, bis-p- (carboxylphenyl ) methane or bis-p- (carboxylphenyl) ethane.

The aromatic dicarboxylic acids are preferred, with terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid being particularly preferred.

Further suitable dicarboxylic acids are those dicarboxylic acids containing -C0-NH groups; these are described in DE-A-2414349. Dicarboxylic acids containing N-heterocyclic rings are also suitable, e.g. those derived from carboxylalkylated, carboxylphenylated or carboxybenzylated monoamine-s-triazine dicarboxylic acids (see DE-A-2121184 35 and 2533675), mono- and bis-hydantoins, optionally halogenated benzimidazoles or parabanic acid. The carboxy-alkyl groups may contain from 3 to 20 C atoms.

Suitable aliphatic diols are the linear and branched aliphatic glycols, in particular those with 2 to 12, in particular 2 to 6, carbon atoms in the molecule, eg: ethylene glycol, 1,2- and 1, 3-propylene glycol, 1,2-, 1,3-. 2,3 ”or 1,4-butanediol, pentyl glycol, neopentyl glycol, 1,6-hexanediol, 1,12-dodecanediol. A suitable cycloaliphatic diol is e.g. 1,4-dihydroxycyclohexane. Further suitable aliphatic diols are e.g. 1,4-bis (hydroxymethyl) cyclohexane, aromatic-aliphatic diols, such as p-xylylene glycol or 2,5-dichloro-p-xylylene glycol, 2,2- (β-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 from 2 to 4 carbon atoms.

Preferred diols are alkylene diols, 1,4-dihydroxy-cyclohexane and 1,4-bis (hydroxymethyl) cyclohexane. Ethylene glycol, 1,4-butanediol as well as 1,2- and 1,3-propylene glycol are particularly preferred.

Further suitable aliphatic diols are the β-hydroxyalkylated, in particular β-hydroxyethylated bisphenols, such as 2,2-bis [4 '- (β-hydroxyethoxy) phenylpropane. Further bisphenols will be mentioned later.

A further group of suitable aliphatic diols are those in the

German Offenlegungsschrift Nos. 1812003, 2342432, 2342372, and 2453326 disclose heterocyclic diols. Examples are: N. N'-bis ^ -hydroxyethyl) -5.5-dimethylhydantoin, N, N'-bis (β-hydroxypropyl) -5,5-dimethylhydantoin, methylenebis [N- (β-hydroxyethyl) -5-methyl- 5-ethyl-25 hydantoin], methylene bis [N- (β-hydroxyethyl) -5,5-dimethylhydantoin], N, N'-bis (β-hydroxyethyl) benzimidazolone, N, N'-bis (β-hydroxyethyl) - (tetrachloro) benzimidazolone or N, N'-bis (β-hydroxyethyl) - (tetrabromo) benzimidazolone.

Suitable aromatic diols are diphenols having a core and in particular two cores, which contain a hydroxyl group on each aromatic core. By aromatic is meant preferably hydrocarbon aromatic groups, such as e.g. phenylene or naphthylene. Besides e.g. hydroquinone, resorcinol or 1.5-. 2,6- and 2,7-dihydroxy-naphthalene should in particular be mentioned those bisphenols, which can be represented by the following formulas: 100 5 6 6 9 11 5 R "FT R" R'1 R ”R” ^ 5 ^ a ~ 00_a_C? "R" R "

20 R R

^ 0 '<^ - ΦΟΗ R "R" 25 R "R" 30 35

The hydroxyl groups can be in the m-position, in particular 1 Π 0 5 6 6 9 12, however in the p-position, R 'and R "in these formulas can be alkyl with 1 to 6 C atoms, halogen, such as chlorine or bromine, especially hydrogen atoms. A may represent a direct bond, or oxygen, sulfur, -SO-, -SO 2 -, C = 0, -P (0) (C 1 -C 20 alkyl) - , optionally substituted alkylidene, cycloalkylidene or alkylene.

Examples of optionally substituted alkylidene are: ethyl 10idene, 1,1- or 2,2-propylidene, 2,2-butylidene, 1,1-isobutylidene, pentylidene, hexylidene, heptylidene, octylidene, dichloroethylidene, trichlorethylidene.

Examples of optionally substituted alkylene are methylene, ethylene, phenylmethylene, diphenylmethylene, methylphenylmethylene. Examples of cycloalkylidene are cyclopentylidene, cyclohexylidene, cycloheptylidene and cyclooctylidene.

Examples of bisphenols are: bis (p-hydroxyphenyl) ether or thioether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, bis (4-hydroxyphenyl) 2,2'-biphenyl, phenylhydroquinone, 1, 2-bis (p-hydroxy-phenyl) ethane, 1-phenyl-bis (p-hydroxyphenyl) methane, diphenyl-bis (p-hydroxyphenyl) methane, diphenyl-bis (p-hydroxyphenyl) ethane, bis (3.5 "di methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) -p-di-isopropylbenzene, bis (3,5-dimethyl-4-hydroxyphenyl) -m-diisopropylbenzene, 2,2 -bis (35'-dimethyl-4'-hydroxyphenyl) propane, 1,1- or 2,2-25 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 (bis-phenol C).

Suitable polyesters of hydroxycarboxylic acids are e.g. polycaprolactone, polypivalolactone or the polyesters of 4-hydroxycyclohexane carboxylic acid or 4-hydroxybenzoic acid.

Also suitable are polymers, which may contain mainly ester bonds, but also other compounds, such as e.g. poly-35 ester amides or polyester imides.

Polyesters with aromatic dicarboxylic acids, especially the polyalkylene terephthalates, are the most important. Therefore, molding compositions according to the invention, wherein the polyester consists of at least 30 mol%, preferably at least 40 mol%, aromatic dicarboxylic acids and 100 5 6 69 13, at least 30 mol / ½, preferably at least 40 mol%, alkylene diols having preferably 2 to 12 carbon atoms are built up, based on the polyester, being preferred.

The alkylene diol in this case is particularly linear and contains 2 to 6 carbon atoms, such as e.g. ethylene, tri-tetra or hexamethylene glycol, and the aromatic dicarboxylic acid is terephthalic and / or isophthalic acid.

Particularly suitable polyesters are PET, PETG (glycol-modified polyethylene terephthalate) or PBT and the corresponding copolymers, with PET and its copolymers being particularly preferred.

Polyketones are meant to be plastics which are produced by polymerizing carbon monoxide with unsaturated hydrocarbons, as described, for example, in EP-A-0222454 or EP-A-0685517.

Advantageous are compositions, as described above, wherein the components (b) and (c) together in an amount of 0.05 to 5 / ί. in particular 0.1 to 5%, for example 0.1 to 2%, based on the weight of the component (a), are present.

Also preferred are compositions wherein the weight-to-20 ratio of components (b): (c) is from 10: 1 to 1:10, especially 5: 1 to 1: 5. for example, 4: 1 to 1: 2.

In addition to components (b) and (c), the compositions according to the invention may contain additional additives or costabilizers include, for example, the following: 25 1 Antioxidants 1.1 Alkylated monophenols. for example 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethyl-phenol, 2,6-di-tert-butyl -4-n-butylphenol, 2,6-di-tert-butyl-4-isobutyl-phenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols, such as eg 2,6-Dinonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundec-1'-ylphenol, 2,4-dimethyl-6- (1'-methylhepta-35 dec-1 ') -yl) phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) phenol and mixtures thereof.

1.2 Alkylthiomethylphenols. for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthio-1 0 0 5 6 6 9 14 methyl-6-ethylphenol, 2,6-didodecylthiomethyl-4 -nonylphenol.

1.3 Hydroquinones and alkrohydroquinones. for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di -tert- 5-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3.5 "di-tert-butyl-4-hydroxyanisole, 3.5" di-tert-butyl-4-hydroxyphenyl stearate, bis- (3.5 Di-tert-butyl-4-hydroxyphenyl) adipate.

1.4 Tocopherols. for example, α-tocopherol, β-tocopherol, y-tocopherol, 6-tocopherol and mixtures thereof (vitamin E).

10 1.5 Hydroxylated thiodiphenyl ethers. for example 2,2'-thio-bis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-buty1-3-methylphenol) 4,4'-Thiobis (6-tert-butyl-2-methylphenol), 4,4'-Thiobis (3,6-di-sec-amylphenol), 4,4'-Bis (2,6-di- methyl 1-4-hydroxyphenyl) disifide.

15 1.6 Alkvlidene bisphenols. for example 2,2'-methylene bis (6-tert-butyl-4-methylphenol), 2,2'-methylene bis (6-tert-butyl-4-ethylphenol), 2,2'-methylene bis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4.6 di-tert-butylphenol), 2,2'-20 ethylidene bis (4,6-di-tert-butylphenol), 2,2'-ethylidene bis (6-tert-butyl-4-isobutylphenol), 2,2'- methylene bis [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 (6-tert-butyl-2-methylphenol), 1,1-bis (5 'tert-butyl-4-hydroxy-2-methylphenyl) butane, 25 2, 6-bis (3 "tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3" tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1.1 -bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3.3_6is (3'-tert-buty1-4'-hydroxyphenyl) butyrate], bis ( 3 "tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-tert 30-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] -terephthalate, 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-dodecyl mercaptobutane, 1,1,5,5-tetra (5 "tert-butyl-4-hydroxy-2-methylphenyl) pentane.

35 1.7 0-. N- and S-benzyl compounds, for example 3.5.3'5 '~ tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3.5 ”dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy ~ 3,5-di- tert-butyl-benzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, 10 5 5 669 15 bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) ditbio terephthalate, bis- ( 3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5 "di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

1.8 Hydroxylated malonates. for example dioctadecyl-2,2-5 bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, didodecyl mercaptoethyl-2 , 2-bis (3,5 "di-tert-butyl-4-hydroxybenzyl) malonate, di [4- (1,1,3,3-tetra-methylbutyl) phenyl] -2,2-bis (3.5" di -tert-butyl-4-hydroxybenzyl) malonate.

1.9 Aromatic hydrogen hydroxide compounds. for example, 1.3.5 "10 tris (3.5" di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5 "di-tert-buty1-4-hydroxybenzyl 2,3,5,6,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.

1.10 Triazine compounds. for example 2,4-bis-octyl mercapto-6- (3.5-di-tert-butyl-4-hydroxyanilino) -1,3.5 "triazine, 2-octyl mercapto 4,6-bis (3.5" di-tert-butyl- 4-hydroxyanilino) -1,5 "triazine, 2-octyl-mercapto-4,6-bis (3.5" di-tert-butyl-4-hydroxyphenoxy) -1,3,5 "triazine, 2.4.6-tris ( 3,5 ~ di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3.5 "tris (3,5" di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5 "Tris (4-tert-butyl-3" hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5 "20 di-tert-buty1-4-hydroxyphenylethyl) -1,3.5" triazine , 1,3,5 "tris (3,5" di "tert-butyl-4-hydroxyphenylpropiony1) hexahydro-1,3,5" triazine, 1.3.5 "tris (3.5" dicyclohexyl-4-hydroxybenzyl) isocyanurate .

1.11 Benzyl phosphonates. for example dimethyl-2,5 "di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,3-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4- hydroxybenzylphosphonate, di-octadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the Ca salt of the monoethyl ester of 3,5 "di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12 Acvlaminophenols. e.g. 4-hydroxylauric anilide, 4-hydroxystearic anilide, N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbamic acid octyl ester.

1.13 Esters of B-f3.5-di-tert-butyl-4-hydroxylphenyl) propionic acid with mono- or polyhydric alcohols, such as e.g. with methanol, ethanol, n-octanol, iso-octanol, octadecanol, 1,6-hexanediol, 1,9_nanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxyethyl ) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3 "thiaundecanol, 3" thiapentadecanol, trimethylhexanediol, trimethylol-propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

, 0 *> * ·. c ^ «Q

3 Q Q ^ b * ^ 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 with methanol, ethanol, n-octanol, iso-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thio-diethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3 "thiapentadecanol, trimethylhexanediol, trimethylolpropane, A-hydroxymethyl-1-phospha-2,6,7-trioxa-bicyclo [2.2.2 ]octane.

1.1 * 3 Esters of 6- (3,5-dicclohexyl- * 1-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, such as e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N ' bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxy-methyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.16 Esters of 3.5-di-tert-butyl- * 1-hydroxylphenyllazic acid with mono- or polyhydric alcohols, such as e.g. with methanol, ethanol, 20 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) oxalic acid diamide, 3 "thiaundecanol, 3-thia-pentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxy-methyl-1-phospha-2,6,7-trioxabicyclo [2.2.2Joctane.

1.17 Amides of 6- (3,6-di-tert-butyl-4-hydroxylphenyl) propionic acid, such as e.g. N, N'-bis (3,5 "di-tert-butyl-4-hydroxyphenylpropionyl} hexamethylene diamide, N, N'-bis (3.5" di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene diamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenyl-propionyl) hydrazide, N. N'-bis [2- (3 ~ [3.5-di-tert-butyl- * 1-hydroxyphenyl] pro-pionyloxy ethyloxoxamide (Naugard® Xl-1 from Uniroyal).

1.18 Ascorbic Acid (Vitamin C).

1.19 Amine antioxidants. such as e.g. N, N'-diisopropyl-p-phenylene-diaraine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethyl-pentyl) -p-phenylenediamine, N , N '- bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N' - dicyclohexyl-p-phenylenediamine, N, N ' -diphenyl-p-phenylenediamine, N, N'-di (2-naphthyl) -pf-enylenediamine, N-isopropyl-N'-phenyl-p-phenylene- 100 5 6 69 17 diamine, N- (1,3-dimethylbutyl ) -Ν'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfonamido) diphenylamine, N, N'-dimethyl-N. N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy diphenylamine, N-phenyl-1-naphthylamine, N- (4-tert- octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. 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 -4-10 dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diamino-diphenylmethane, Ν, Ν, Ν ', 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, tert-octylated N-phenyl-1 -naphthylamine, mixture of mono- and di-alkylated tert-15-butyl / tert-octyldiphenylamines, mixture of mono- and di-alkylated nonyldiphenylamines, mixture of mono- and di-alkylated dodecyl-diphenylamines, mixture of mono- and di-alkylated isopropyl / isohexyl diphenylene amines, mixture of mono- and di-alkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-diroethyl-4H-1,4-benzothiazine, phenothiazine, mixture of mono- and di-alkylated tert-butyl / tert-octylphenothiazines, mixture of mono and di-di alkylated tert-octyl-phenothiazines, N-allylphenothiazine, Ν, Ν, Ν ', N'-tetraphenyl-1,4-diamino-but-2-ene, N, N-bis (2,2,6,6-tetramethylpiperidine -4-yl) hexamethylenediamine, bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6- tetramethylpiperidin-4-ol.

2. UV absorbers and light protectors 2.1 2- (2 '-hydroxyphenylbenztriazoles. Such as 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 ) benzo triazole, 2- (3'5'-di-tert-butyl-2'-hydroxyphenyl) -5-chloro-benzo triazole, 2- (3'-tert-butyl-2'-hydroxy-5 1'-methylphenyl) -5-chloro-benzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3'5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis- (a, a-dimethylbenzyl) -2'-hydroxyphenyl} benzotriazole 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyl-oxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5'- [2 - (2-ethyl hexyl oxy) carbonylethyl] -2 '-hydroxyphenyl) - 5-chlorobenzo-1 0 5 5 6 69 18 triazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2-methoxycarbonylethyl} phenyl) -5-chlorobenzotri azole, 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'-5 [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy -5'-methylphenyl) benzotriazole and 2- (3'-tert-butyl-2 '-hydroxy-5' - (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3 "tetramethylbutyl) 6-benz triazol-2-yl-phenol]; the transesterification product of 2- [3'-tert-butyl-5 '- (2-methoxy-10-carbonylethyl) -2'-hydroxyphenylbenzotriazole with polyethylene glycol 300; [R-CH2CH1-C00-CH2CH2] .- with R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl; 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 '- (α, α-dimethylbenzyl) phenylbenzotriazole. 15 2.2 2-hydroxylbenzophenones. such as, for example, the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4-trihydroxy, 2'-hydroxy-4, 4'-dimethoxy derivative.

2. λ Esters of optionally substituted benzoic acids. such as, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl-20 salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert - butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid-2 -methyl-4,6-di-tert-butylphenyl ester.

25 2.4 Acrvlaten. such as, for example, α-cyano-β, β-diphenylacrylic acid ethyl ester, respectively. isooctyl ester, α-carbomethoxy cinnamic acid methyl ester, α-cyano-ft-methyl-p-methoxy cinnamic acid methyl ester, respectively. -butyl ester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N- (1-carbomethoxy- (1-cyanovinyl) -2-methylindoline.

30 2.5 Nickel compounds. such as, for example, nickel complexes of 2,2'-thiobis [4- (1,1,3,3 "tetramethylbutyl) phenol], such as the 1: 1 or 1: 2 complex, optionally with additional ligands, such as n-butylamine , triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyl dithiocarba size, nickel salts of the monoalkyl esters, eg the methyl or ethyl 35 ester, of 4-hydroxy-3.5 "di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenyl undecyl-ketoxime, nickel complexes of 1-phenyl-4-lauroyl- 5-hydroxypyrazole, optionally with additional ligands.

100 5 6 69 19 2.6 Sterically hindered amines. such as, for example, bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) sebacate, bis {1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, n-butyl-5 3,5-di-tert-butyl-4-hydroxybenzylmalonic acid bis ( 1,2,2,6,6-pentamethyl-piperidyl) ester, the condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-10 triazine, tris (2,2,6,6- tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetraraethyl-4-piperidyl) -1,2,3,4-butane tetraoate, 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 (1,2,6,6,6 pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5 ~ 15 di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9 "tetramethyl-1,3.8" t riazaspiro [4. 5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, linear or cyclic condensation products of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-di-chloro-1,3,5 "triazine, the condensation product of 2-chloro-4,6-di (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3.5 "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 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3 dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl ) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-penta-methyl-4-piperidyl) pyrrolidine-2,5-dione, 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 4-cyclohexylamino-2,6-dichloro- 1.3 "t riazine, 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 (CAS Reg. No. [136504-96-6]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 2- Undecyl-7,7,9-9-tetramethyl-1-qxa-3,8-diaza-4-oxospiro [4,5] decane, the orazetting product of 7.7.9.9-tetramethyl-2-cycloundecyl-1-oxa-3, 8-diaza-4-oxospiro [4,5] decane and epichlorohydrin, 1,1-bis (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethylene, N, N'-100 5 6 69 20 bis-formyl-N, N'-bis {2,2,6,6-tetramy 1-4-piperidyl) hexamethylene diamine, the diester of 4-methoxymethylene malonic acid with 1, 2,2,6,6-pen tamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl) Siloxane, the reaction product of maleic anhydride 5 α-olefin copolymer and 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7 Oxalic acid diamides. such as, 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'-ethyl-oxanilide, N.N'-bis (3 "dimethylaminopropyl) oxalamide, 2-ethoxy-5" tert-butyl-2'-ethyl oxanilide and the mixture thereof with 2- ethoxy-2'-ethyl-5, 4 '-di-tert-butyloxanilide, mixtures of o- and p-methoxy as well as o- and p-ethoxy di-substituted oxanilides.

2.8 2- (2-hydroxypropyl) -1,5-triazines. such as, for example, 2,4,6-15 tris (2-hydroxy-4-octyloxyphenyl) -1,3.5 "triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4- dimethylphenyl) -1,3.5 "triazine, 2- (2,4-dihydroxy-phenyl) -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-4-20 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- dimethyl) -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-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis {2,4-dimethylphenyl) -1,3.5 "triazine, 2- [2-hydroxy-4 - (2-hydroxy-3 "dodecyloxy-propoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3.5" triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6 -diphenyl-1,3.5 "Triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5" triazine, 2,4,6-tris [2-hydroxy-4- (3 "30 butoxy-2 -hydroxypropoxy) phenyl] -1,5 "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. such as, for example, N, N'-diphenyloxal-35 acid diamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyl-oyl) hydrazine, N, N'-bis (3.5 ”di-tert-butyl-4 -hydroxyphenylpropionyl) -hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalic acid dihydrazide, oxanilide, isophthalic acid dihydrazide, sebacic acid - v. λ 5 5 δ 3 21 bisphenyl hydrazide, N, N'-diacetyladrazide N, N'-bis-salicycloyloxalic acid dihydrazide, N, N'-bis-salicyloylthiopropionic acid dihydrazide.

4. Phosphites and Phosphonites. such as, for example, triphenylphosphite, diphenylalkylphosphites, phenyl dialkylphosphites, tris (nonylphenyl) phosphite, trilaurylphosphite, trioctadecylphosphite, distearylpentaerythritol diphosphite, tris (2,4-di-tertyl-butylphenyl) phenyl) phenyl -tert-butylphenyl) pentaerythritol diphosphite, bis- (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis-iso-decyl oxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methyl-phenyl ) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythri toldiphosphite, tristearyl sorbi toltriphosphite, tetrakis {2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isooctyloxy-2, 4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12- methyl-dibenz [d, g] -1,3,2-dioxaphosphocine, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bis (2,4-di-tert-butyl-6-methylphenyl ethylphosphite, 2-ethylhexyl- (3.3'-5.5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite.

5. Hvdroxvlamines. such as, for example, Ν, Ν-dibenzylhydroxylamine, 20 Ν, Ν-diethylhydroxylamine, Ν, Ν-dioctylhydroxylamine, Ν, Ν-dilaurylhydroxylamine, Ν, Ν-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine-amine hexadecyl-N-octadecylhydroxyl-amine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine from hydrogenated tallow fatty amines.

6. Ni-thrones, such as, for example, N-benzyl-alpha-phenyl-nitron, Ν'-ethyl-alpha-methyl-nitron, N-octyl-alpha-heptylni tron, N-lauryl-alpha-undecylnyl, N-tetradecyl-alpha -tridecylnitron, N-hexadecyl-alfa-pentadecyl-nitron, N-octadecyl-alpha-heptadecyl-nitron, N-hexadecyl-alpha-heptadecyl-nitron, N-octadecyl-alpha-pentadecyl-nitron, N-heptadecyl-30-alpha-heptadecyl alpha-hexadecylnitron, nitrons derived from Ν, Ν-dialkylhydroxylamines prepared from hydrogenated tallow fatty amines.

7. Thio synergists. such as, for example, thiodipropionic acid dilauryl ester or thiodipropionic acid distearyl ester.

8. Peroxide-destroying compounds, such as esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide fi fi 9 22 pentaerythritol tetrakis ((i-dodecyl mercapto propionate.

9. Stabilizers for polyamide, such as, for example, copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

5 10. Basic co-stabilizers. such as, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg behenate, Mg stearate, sodium ricinoleate, K-10 palmitate, antimony pyrocatecholate or zinc pyrocatecholate.

11. Nucleating agents, such as, for example, inorganic dusts, such as e.g. talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably alkaline earth metals; organic compounds such as mono or polycarboxylic acids, as well as their salts, such as e.g. tert-butyl benzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymers, such as e.g. ionic copolymers ("ionomers").

12. Fillers and reinforcing agents, such as, for example, calcium carbonate, silicates, glass fibers, glass balls, talc, kaolin, 20 mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers from other natural products, synthetic fibers .

13. Other additives, such as, for example, plasticizers, lubricants, emulsifiers, pigments, Theology additives, catalysts, conversion aids, optical brighteners, flame retardants, anti-static agents and blowing agents.

1 ^ J. Benzo Furanone reso. indolinones. such as, for example, those described in US-A-4325863. US-A-i433824it, US-A-5175312, US-A-52I6O52, US-A-5252643. DE-A-4316611, DE-A-43I6622, DE-A-4316876, EP-A-30 Ο589839 or EP-A-O59IIO2, or 3 - [^ "(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-butyl-benzo-Fu ran-2-one, 3_ (3,5-dimethyl-14-pivaloyloxy-phenyl) -5,7-di-tert-butylbenzo-furan-2-one, 3- (3-dimethylphenyl) -5,7-di-tert-butylbenzo-

Furan-2-one, 3 "(2,3" dimethylPhenyl) -5,7-di-tert-butylbenzoFuran-2-one.

The cost stabilizers, with the exception of the benzofuranones mentioned under item 14, are added, for example, in concentrations of 0.01 to 10%, based on the total weight of the polyamide, polyester or polyketone to be stabilized. .

Preferred further compositions contain, in addition to the components (a), (b) and (c), further additives, in particular phenolic antioxidants, light protection agents and / and processing stabilizers.

Particularly preferred additives are phenolic antioxidants (number 1 in the list), sterically hindered amines (number 10 2.6 in the list), phosphites and phosphonites (number 1 in the list) and peroxide-destroying compounds (number 8 in the list).

Particularly preferred additional additives (stabilizers) are benzofuran-2-ones, which, e.g. in US-A-A325863, US-A-4338244, US-A-5175312, US-A-5216052, US-A-52526 ^ 3. DE-A-43166H, DE-A-4316622, DE-A-316876, EP-A-O589839 and EP-A-O59IIO2 are described.

Examples of such benzofuran-2-ones are compounds of the formula I'5 20 XXc> o R '> I fS-R', 2 h ”25 wherein R '' means an unsubstituted or substituted carbocyclic or heterocyclic aromatic ring system; R'12 is hydrogen; R 4 is hydrogen, alkyl of 1 to 12 carbon atoms. cyclopentyl, cyclo-30 hexyl or chlorine; _.

R ", 3 has the meaning of R'12 or R'j /, or a group of the formula

O

II

- (CH2) s-C-OR'16, 35

It · © 5 6 ss 2k

o O O

II II II

- (CH2) rC-N {R17) 2, - (CH2) ~ C — O — A— O — C— (CH2), - E, O O o o

II II II II

- (CH2) 5-C-NR ·, -A-NR ', - C- (CH2) s-E. - (CH2) rC-NR'1T-A-O-C-CCH2 -E.

5 O Y_ o o

- (CH2) s-C-N-C-(CH2) -E. -CHj-S-R ', 9, - CH (C6H5) -C-OR-, 6 -D-E

wherein 10 R 'is 6 hydrogen, alkyl of 1 to 18 carbon atoms, alkyl of oxygen or sulfur interrupted alkyl of 2 to 18 carbon atoms, dialkylaminoalkyl of a total of 3 to 16 carbon atoms, cyclopentyl, cyclohexyl, phenyl or with 1 to 3 alkyl groups having phenyl substituted at most 18 carbon atoms together; 15 s is 0, 1 or 2; the substituents R'17 independently of one another are hydrogen, alkyl of 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, with 1 or 2 alkyl groups of phenyl substituted at most by 16 carbon atoms, a group of the formula-formule ^ Ο ,, ΟΗ, -C2H2, -0-CtH2l *, or 20 O

II

-C 1 -H 2 -O-C-R '20 or together with the nitrogen atom to which they are attached form a piperidine or morpholine group; t is 1 to 18; R1 is hydrogen, alkyl of 1 to 22 carbon atoms or cycloalkyl of 5 to 12 carbon atoms; A is an alkylene optionally interrupted by nitrogen, oxygen or sulfur with 2 to 22 carbon atoms; R 1 'is hydrogen, alkyl of 1 to 18 carbon atoms, cyclopentyl, cyclo-hexyl, phenyl, with 1 or 2 alkyl groups of phenyl or benzyl substituted at most 16 carbon atoms; R 19 is alkyl of 1 to 18 carbon atoms; D is -O-, -S-, -SO-, -SO2- or -C (R'21) 2; the substituents R'21 independently of one another are hydrogen or C 1 -C 16 alkyl 35, the two substituents R'2] together being 1 to 16 carbon atoms

II

or R'2J phenyl or a group of the formula - (CH2) s-C-0R ', g or 100 5 6 69 25

O

II

- (CH2) is 8-C-N (R'17) 2, wherein s, R'jê and R'17 have the meanings shown above; 5 E is a group of the formula R'15 tTjI-) = ° 10 / l 1NR'it, where R'n, R'i2 and R'^ have the meanings shown above; and R'15 hydrogen, alkyl of 1 to 20 carbon atoms, cyclopentyl, cyclo-O

II

hexyl, chlorine or a group of the formula -CH2 -C-OR'16 or 20 O

II

-CH 2 -C-N (R'17) 2, where R'16 and R'17 have the meanings shown above, or R'15 together with R'n forms a tetramethylene group.

Those benzofuran-2-ones are preferred, wherein R'13 is hydrogen, alkyl of 1 to 12 carbon atoms, cyclopentyl, cyclohexyl, chlorine or

II II

a group of the formula - (CH2) ^ - C-OR '16, - (CH2) SCN (R'17) 2 or -DE 30, where s, R' ^, R'i7, D and E are the above have the meanings shown, wherein R'16 has in particular the meaning hydrogen, alkyl of 1 to 18 carbon atoms, cyclopentyl or cyclohexyl.

Furthermore, those benzofuran-2-ones are preferred, wherein R 1 is phenyl or phenyl substituted with 1 or 2 alkyl groups with at most 12 carbon-35 atoms; R'1Z is hydrogen; R '1 is hydrogen or alkyl of 1 to 12 carbon atoms; 0

II

R'13 hydrogen, alkyl of 1 to 12 carbon atoms, - (CH2) e-C-OR '! 6, 40 0

II

- (CH2) S-C-N (R'17) 2 or -D-E; R'15 hydrogen, alkyl with 1 to 20 10 0 5 6 6 9 26

O O

II II

carbon atoms, -CH2-C-OR'16 or -CH2-CN (R '1?) 2 or R'15 together with R'n form a tetramethylene group, where s, R'16, R'17 <D and E have the meanings shown in 5 at the beginning.

Also of particular interest are those benzofuran-2-ones, wherein R'13 is hydrogen, alkyl of 1 to 12 carbon atoms or -D-E; R'12 and R'n are independently hydrogen or alkyl of 1 to 4 carbon atoms; and R'15 is alkyl of 1 to 20 carbon atoms, D and 10E having the meanings initially indicated.

Also of particular interest are, finally, those benzofuran-2-ones, wherein R'ys is alkyl of 1 to k carbon atoms or -D-E; R'12 and R '' are hydrogen; and R'J5 alkyl of 1 to 4 carbon atoms, cyclopyl or cyclohexyl, where D is a group -C (R'21) 2- and E is a group 15 of the formula R'1

TjT °> = or \ 2 hk ”, where the substituents R'21 are the same or different and each are alkyl of 1 to 4 carbon atoms and R'n, R ', 2, R' ^ and R'j are the have meaning.

The amount of additional benzofuran-2-ones used can vary within wide limits. For example, they may be present in the compositions of the invention for 0.0001 to 5, preferably 0.001 to 2, especially 0.01 to 2% by weight.

The processing of the components (b) and (c) as well as any further additives in the component (a) [polyamide, polyester or poly-ketone] is done by known methods, for instance before or during the molding or also by application of the dissolved or dispersed components (b) and (c) on component (a), optionally with subsequent evaporation of the solvent. The components (b) and (c) can also be added to the materials to be stabilized [component (a)] in the form of a masterbatch containing, for example, a concentration of 2.5 to 25% by weight.

The components (b) and (c) can also be used before or during the polymerization. r S a f> 9 tl · '· V · ""' 27 sation or before crosslinking.

The components {b) and (c) can be incorporated in the component (a) to be stabilized in pure form or encapsulated in waxes, oils or polymers.

The components (b) and (c) can also be sprayed on the component (a) to be stabilized. They are capable of other additives (e.g., the conventional additives shown above), respectively. dilute their melts so that they can also be sprayed together with these additives on the component (a) to be stabilized.

Particularly advantageous is the addition by spraying during the deactivation of the polymerization catalysts, e.g. the steam used for deactivation can be used for spraying.

The polyamides, polyesters and polyketones thus stabilized can be used in very different forms, e.g. as films, fibers, straps, molding compounds, profiles or as a binding agent for lacquers, glues or kits.

Components (b) and (c) are particularly suitable as processing stabilizers (heat stabilizers). For this, they are advantageously added before or during the processing of the component (a).

A preferred embodiment of the present invention is therefore the use of the phosphite of the formula I and at least one compound of the formula II as stabilizers, in particular processing stabilizers (thermo-stabilizers), for polyamides, polyesters or polyketones against oxidative, thermal or light-induced breakdown.

The components (b) and (c) are distinguished by an advantageous coloring behavior, i.e. little discoloration of the polyamides, polyesters and polyketones, during processing.

The present invention also relates to a process for stabilizing a polyamide, polyester or polyketone against oxidative, thermal and / or light-induced degradation, which is characterized in that the phosphite of the formula I and at least one compound with "incorporates or applies Formula II to it.

The present invention also relates to a stabilizer mixture containing (i) the phosphite of the formula I and (ii) at least 100 5 6 69 28 of a compound of the formula II.

Stabilizer mixtures are also preferred, in which the weight ratio of the components (i) :( ii) is 10: 1 to 1:10, in particular 5: 1 to 1: 5, for example 4: 1 to 1: 2.

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

The stabilizer mixtures of components (i) and {ii) are referred to as "LC blends" ("Low Color Blends"). They are distinguished by excellent storage stability, low volatility and excellent free flowing properties. The LC blends listed in Table A are especially preferred.

15 Table A: LC blend Component (i) Component {ii) Weight ratio (i): (ü) 20 A Irgafos®12a "Irganox® 1010b" 1: 1 B Irgafo ^ B) 12 ""! Irganox® 1010b 1 2: 1 C Irgafo ^ © 12'J J Irganox® 1010b 1 1: 2 25 ------ D Irgafo ^ B) 12H 1 Irganox® 1010b ’4: 1 E Irgafo ^ E) 12fi! Irganox® 3H ^ rl 1: 1 30 F IrgafoS®121 Irganox® 1098 "1 1: 1 G Irgafo ^ © 12a 1 Irganox® 109δ [| 1 1: 2 H Irgafo ^ S) 12a 'Irganox® 1076' 1 4: 1 35 ----- I Irgafoö © 12a1 Irganox® 1076 ') 2: 1 a) Irgafoö® 12 corresponds to the compound of the formula I.

b) Irganox® 1010 corresponds to the compound of formula IIc.

C) Irganox® 3114 corresponds to the compound of the formula lig.

d) Irganox® 1098 corresponds to the compound of the formula Ha.

e) Irganox® 1076 corresponds to the compound of the formula Ilb.

The invention is further illustrated in the following examples. 45 Partial or percentage data refer to weight.

100 5 6 63 29

Example I: Stabilization of polyamide-6.

100 parts of unstabilized polyaraide-6 granulate (Ultramic®33. BASF) was pulverized by cryogenic grinding and mixed with the stabilizers shown in Table B 5. The mixture is mixed with a Henschel mixer for 2 minutes. The powder thus obtained is then dried at 80 ° C for 6 hours and then extruded at an extruder (type Berstoff) at a maximum of 240 ° C and then granulated. The resulting granulate is injected into 1.0 mm thick dumbbells and 2.0 mm thick plates in an injection molding machine at a maximum of 240 ° C.

The dumbbells are aged at 140 ° C in an oven with air circulation. Aging progress is followed by the determination of the force-elongation diagrams in distances of 1-3 days. That time is defined as the end point, after which the elongation at rest decreases to 50% of the initial value. The longer the time, the better the stabilization. The results are summarized in Table B.

The plates are aged in an air-circulating oven for 1500 hours at 80 ° C. The Yellowness Index (YI) of these plates is determined according to ASTM D 1925-70. Low YI values mean little discoloration, high YI values strongly discolor the patterns. The smaller the discoloration, the more effective the stabilizer mixture. The results are summarized in Table B.

25 Table B:

Example Stabilizer Time in hours to a Yellowness Index

residual elongation after 1500 hours at 50% at 140 ° C 80 ° C

30 (Dumbbells) (Plates)

Ia - 12 51.5 0.2% Irgafod® l68a "35 Ib 282 50.0 0.2% Irganok® 1098" "0.2% Irgafos® 12r"

Ic 369 42.0 40 0.2% Irgano (S) 10981 ”1 10 0 5 6-58

Irgafo® 168 (Ciba-Geigy) means tris (2,1-di-tert-butylphenyl) -phosphite.

B) Irganox® 1098 (Ciba-Geigy) means N.N'-bis (3.5 "di-tert-butyl-9-hydroxyphenylpropionyl) hexamethylenediamine (compound of the formula

Ila).

5 Γ H3C

\ / CH3

/ C

- K y HO— (v /) CH2 — CH — C —NH- (CH2) 3-- V f / 22 '2/3 (Ha) 10 / ^ ch3 h3c 3 L 3 j 2 15 c) Irgafos® 12 (Ciba-Geigy) means 2,2 ', 2 "-nitrilo [triethyl-tris- (31 3', 5.5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite] Chemical Abstract "Registry" number: 8091-10-33_9 and represents the compound of formula I.

20 (0Η3) 30 C (CHa) 3 P-0-CH2CH2 - Ν (|) 25 JTV0

(C Η3) 3C

C (CH3) 3 J3 The results of table B show that the stabilizer mixture according to the invention (example Ic) is clearly more effective than the known stabilizer mixture (example Ib).

I = 100 5 6 69

Claims (17)

A composition containing a) an oxidative, thermal or light-induced degradation 5 polyamide, polyester or polyketone, b) the phosphite of the formula I (ch3) 3c C (CH3) 3 10] P - O - CH. CH, - N m Ir ° C (CH3) 3 LJ 3 15 and c) at least one compound of the formula II 20 Γ ”1 20 \ / CH3 H3C \ / = \ (") HO - (\ /) - X - R 2 R 25 n where R 1 represents C 1 -C 2 alkyl, n represents 1, 2, 3 or 4, 30 0 0 II II X methylene, -CH2-CH2-CY- or -CH2-C-0- CH 2 -CH 2 -, Y is oxygen or -NH-; and when n is 1, 35 O II represents X -CH 2 -CH 2 -CY-, wherein Y is attached to R2 and R2 is C 1 -C 25 alkyl; and if n 2, 10 is 0. 5 6 69 O II X -CH 2 -CH 2 -CY-, wherein Y is attached to R 2 and R 2 is C 2 -C 12 alkylene, C 1 -C 12 alkylene interrupted by oxygen or sulfur, 5 or as Y - NH- means, R2 additionally represents a direct bond; and when n is 3, O II X represents methylene or -CH2 -C-O-CH2-CH2-, where the ethylene group is 10 attached to R2 and <v - ^ ° Rt. 1 I; and i5 o if n is 4, 0 20 || X represents -CH2-CH: -C-Y- wherein Y is attached to R2 and R2 represents C1 -C10 alkane tetrayl. 2. A composition according to claim 1, which contains as component (c) at least one compound of the formula II, wherein, when η is 1, R 2 represents C 1 -C 20 alkyl. A composition according to claim 1, which contains as component (c) at least one compound of the formula II, wherein when n is 2, R 2 is C 2 -C 8 alkylene, C 1 -C 8 alkylene interrupted by oxygen or sulfur; or, when Y represents -NH-, R2 additionally represents a direct bond; and if n is i), R 2 represents C 1 -C 6 alkane tetrayl. A composition according to claim 1, which contains as component (c) at least one compound of the formula II, wherein R 1 represents methyl or tert-butyl, 40 n is 1, 2 or 4, I: 100 5 6 6§ O II X represents -CH2-CH2-CY-, Y represents oxygen or -NH-; and 5 when η is 1, R 2 represents 0 ^ -0.8 alkyl; and when n is 2, R 2 represents C 1 -C 6 alkylene or oxygen-interrupted C 4 -C 5 alkylene; and 10 when n is 4, R 2 represents Ca-Cl, alkane tetrayl. The composition according to claim 1, wherein the component (c) contains at least one compound of the formula Ha, Ilb, IIc or member H, C / CH3 X H3C K-II HO - (v /) - CH2-CH? -C - NH- (CHJ, - V '/ 22 ^ (Ha) HX ^ / 7 CH3 h3c 3 L 3 J 2 h3c / CH3 -K ii HORyi-ch2-ch-c-o-c „h3, (Ilb) HC ^ / / CH_ h3c 3 i 0 0 5 6 6 9 H, C 3 \ ^ ch3 \ _ yy 5 H 2 -V V-CH -CH-C 0 CH 2 C 1 -C 1 H 3 C-c; / CH, L h3c j4 10 H, C 3 \ / CH3 H CA ° 3) = \ II (member) HO - / x /) - CH —CH —CO-CH — CH — o — CH2-- 15) - "H, CL means 3 J 2 20. The composition of claim 5. wherein the component (c) represents a compound of the formula Ila, Ilb or IIc. A composition according to claim 1, wherein the polyamide is polyamide-6, polyamide-6,6, polyamide-11 or polyamide-12 or a copolymer thereof. The composition of claim 1, wherein the polyester is PET, PETG or PBT or a copolymer thereof. The composition of claim 1, wherein the components (b) and (c) together in an amount of 0.05 to 5%. based on the weight of component (a). 35 The composition of claim 1, wherein the weight ratio of the components (b) :( c) is from 10: 1 to 1:10. I o o 5 a $ u A composition according to claim 1, which additionally contains components in addition to components (b) and (c). 12. A composition according to claim 11, which additionally contains phenolic antioxidants, light protection agents and / and processing stabilizers. The composition according to claim 11, which further contains at least one compound of the benzofuran-2-one type. 10 1 ^. Use of the phosphite of the formula I and at least one compound of the formula II as defined in claim 1 as stabilizers for polyamides, polyesters or polyketones against oxidative, thermal and / or light-induced degradation. 15 Use according to claim 11 as processing stabilizers. 16. Process for stabilizing a polyamide, polyester or polyketone against oxidative, thermal and / or light-induced degradation, characterized in that it comprises the phosphite of the formula I and at least one compound of the formula II, such as these claim 1 are defined, incorporated or applied thereto. A stabilizer mixture comprising (i) the phosphite of the formula I and (ii) at least one compound of the formula II as defined in claim 1. The stabilizer mixture according to claim 17. wherein the weight ratio of the components (i) :( ii) is from 10: 1 to 1:10. 10 0 5 6 6 9