ITMI970732A1 - STABILIZATION OF A POLYAMIDE OF A POLYESTER AND OF A POLYCETONE - Google Patents

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 phenol which has a spherical impediment, it relates to their use for the stabilization of a polyamide, of a polyester or a polyketone against oxidative, thermal and / or light-induced degradation and also relates to a process for the stabilization of these plastic materials.

From U.S. Pat. 4,360,617 it is known that mixtures of stabilizers containing symmetrical triarylphosphites and certain phenolic antioxidants are particularly well suited to protect certain organic products such as for example polyurethane, polyacrylonitrile, polyamide-12 or polystyrene from oxidative, thermal or light-induced degradation. Tris (2,4-di-tert.-butylphenyl) -phosphite (Irgafos® 168, Ciba-Geigy) is described as the preferred symmetrical triarylphosphite.

These known stabilizer mixtures, in polyamides, polyesters and polyketones, may not meet all the established requirements. It is known that such stabilizer mixtures decrease the initial color and color development of the polyamide during aging in the oven and decrease the worsening of the mechanical properties of the polyamide during aging in the oven and during irradiation. As a drawback of these stabilizer mixtures it is often observed that these phosphites tend to form efflorescence.

In U.S. Pat. 4,318,845 and 4,374,219 alkanolamine esters of cyclic 1,1'-biphenyl-2,2'-diyl-phosphites and alkylidene-1,1'-biphenyl-2,2'-diyl-phosphites are described as stabilizers for organic polymers and for lubricating oils, in particular as stabilizers for the processing of polyolefins, elastomers, polyesters and polycarbonates.

It has now been found that a stabilizer mixture containing an entirely determined phosphite selected from U.S. Pat. Nos. 4,318,845 and 4,374,219, together with a wholly determined group of phenols exhibiting steric hindrance, is particularly well suited as stabilizers for polyamides, polyesters or polyketones. The polyamides, polyesters or polyketones thus stabilized have improved properties as regards oxidative, thermal or / and light-induced degradation. The phosphite according to the invention is not expelled as efflorescence.

The present invention therefore relates to compositions containing

a) a polyamide, a polyester or a polyketone subjected to oxidative, thermal or light-induced degradation,

b) the phosphite of formula I

in which

Ri represents C1-C4-alkyl,

n stands for 1, 2, 3 or 4,

X represents methylene,

Y is oxygen or -NH-; And

when n stands for 1,

X represents, Y being bonded to R2 and R2 is C 1 -C25-alkyl; And

when n is 2,

X represents Y being bonded to R2, and Rz indicates C2-Ci2-alkylene, C4-Ci2-alkylene interrupted by oxygen or by sulfur; or, when Y indicates -NH-, R2 also represents a direct bond; and when n is 3,

X represents methylene or the ethylene group being bonded to R2, e

when n is 4,

X represents Y being bonded to R2, and R2 denotes C4-Ci0-alkantetrayl.

Alkyl with up to 25 carbon atoms indicates a branched or unbranched radical such as for example methyl, ethyl, propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1.1.3.3-tetramethylbutyl, 1-methylptyl, 3-methylptyl, 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 Ri is methyl and tert.-butyl. a particularly preferred meaning of R2 is C1 ~ C20-alkyl, in particular C1-Cm-alkyl, for example C1-Cie-alkyl. A particularly preferred meaning of R2 is CB-Ci8-alkyl, in particular C14-Cie-alkyl, for example C18-alkyl.

C2-C 2-alkylene indicates a branched or unbranched radical, for example ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene or dodecamethylene. A preferred meaning of R2 is for example C2-C10-alkylene, in particular C2-C8-alkylene. A particularly preferred meaning of R2 is for example C4-C8-alkylene, in particular C4-C6-alkylene, for example hexamethylene.

C4-Ci2-alkylene interrupted by oxygen or by sulfur can be interrupted once or several times

A preferred meaning of R2 is for example C4-C8-alkylene interrupted by oxygen or by sulfur, in particular C4-C8-alkylene interrupted by oxygen or by sulfur, for example C4-C 1 -alkylene interrupted by oxygen or by sulfur. A

Alkantetrayl with 4 to 10 carbon atoms

pentaerythrityl.

In the case of component (c) it can also be mixtures of different phenols with steric hindrances, of formula II.

There are interesting compositions containing, as component (c) at least one compound of formula II, in which, when n is 1, R2 represents C1-C20-alkyl.

Preferred are compositions containing as component (c) at least one compound of formula II, wherein

when n is 2,

R2 represents C2-Ca-alkylene, C 1 -CB-alkylene interrupted by oxygen or by sulfur; or when Y represents -NH-, R2 also represents a direct bond; And

when n is 4,

R2 represents C '-C8-alkantetrayl.

Likewise, compositions containing as component (c) at least one compound of formula II, wherein

Ri represents methyl or tert.-butyl,

n stands for 1, 2 or 4,

0

X represents

Y indicates oxygen or -NH-; And

when n stands for 1,

R2 represents C 4-C 8-alkyl; And

when n is 2,

R2 represents C4-C6-alkylene or C4 ~ C6-alkylene interrupted by oxygen; And

when n is 4,

R2 represents C4-C3-alkantetrayl.

Equally interesting are compositions which contain as component (c) at least one compound of formula I, wherein the compound of formula I indicates a compound of formula IIa to Uh

Irganox® 1098, Irganox® 1076, Irganox® 1010 <">, Irganox® 245, Irganox® 259, Irganox® 3114, Irganox® 1035 and Irganox® 3125 are protected trade names of the Company Ciba-Geigy.

Preferred are compositions containing as component (c) at least one compound of formula I, wherein the compound of formula I is a compound of formula IIa, IIb, Ile or Ild, in particular it is a compound of formula IIa, Ilb or Ile, for example a compound of formula IIa.

Component (b) of the composition according to the invention, or the phosphite of formula I is known and its preparation is described in U.S. Pat.

4,318,845 and 4,374,219 mentioned at the beginning, in Example 4. This phosphite can be present in various modifications, as described for example in U.S. Pat. that follow. U.S. 5,276,076 discloses a solid amorphous form of the phosphite of formula I. 5,334,739 describes the α-crystalline form of the phosphite of formula I. 5,326,802 discloses the β-crystalline form and U.S. 5,321,031 describes the γ-crystalline form of the phosphite of formula I. The phosphite of formula I is commercially obtainable under the protected name Irgafos® 12 (Ciba-Geigy).

Component (c) of the composition according to the invention, or the compounds of formula II are known and are partially commercially obtainable. Possible preparation processes for compounds of formula II can be found, for example, in U.S. Pat. 3,330,859 or 3,960,928.

By polyamides we mean polyamides or aliphatic and aromatic copolyamides deriving from diamines and dicarboxylic acids and / or aminocarboxylic acids or their 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 also amorphous polyamides of the Trogamid type PA 6-3-T and Grilamid TR 55. Polyamides of the indicated type are generally known and obtainable on the market.

There are interesting compositions containing 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 elastomers or polyamide 6.6 mixed with polypropylene.

In the case of the polyesters, they may be homopolyesters or copolyesters deriving from dicarboxylic acids and from aliphatic, cycloaliphatic or aromatic diols or from hydroxycarboxylic acids.

Aliphatic dicarboxylic acids can contain 2 to 40 carbon atoms, cycloaliphatic dicarboxylic acids can contain 6 to 10 carbon atoms, aromatic dicarboxylic acids can contain 8 to 14 carbon atoms, aliphatic hydroxy carboxylic acids can contain 2 to 12 carbon atoms and aromatic hydroxy carboxylic acids and also cycloaliphatic hydroxy carboxylic acids can contain 7 to 14 carbon atoms.

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

Aromatic diols are indicated those in which two hydroxyl groups are connected to one radical of an aromatic hydrocarbon or to different radicals of aromatic hydrocarbons.

Furthermore, it is possible that the polyesters are branched with small amounts, for example 0.1 to 3 mol%, referred to the dicarboxylic acids present, of more than bifunctional monomers (for example pentaerythritic acid, trimellitic acid, 1,3,5-tri (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 can be statistically divided or they can be block polymers.

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

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

As cycloaliphatic dicarboxylic acids, the following are considered: 1,3-cyclobutanbicarboxylic acid, 1,3-cyclopentanbicarboxylic acid, 1,3- and 1,4-cyclohexanbicarboxylic acid, 1,3- and 1,4- (dicarboxylmethyl) -cyclohexane, 4,4'-dicyclohexylbicarboxylic acid.

Suitable aromatic dicarboxylic acids are considered: in particular terephthalic acid, isophthalic acid, o-phthalic acid and also 1,3-, 1,4-, 2,6- or 2,7-naphthalene-dicarboxylic acid, 4,4 '-diphenylbicarboxylic acid, 4, 4' -diphenylsulfonbicarboxylic acid, 4,4'-benzophenonbicarboxylic acid, 1,1,3-trimethyl-5-carboxyl-3- (pcarboxylphenyl) -indane, 4,4'-diphenyletheredicarboxylic acid, bis- p- (carboxylphenyl) -methane or bisp- (carboxylphenyl) -ethane.

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

Further suitable dicarboxylic acids are those which contain -CO-NH- groups; they are described in DE-A-2.414.349. Also suitable are dicarboxylic acids that contain N-heterocyclic rings, for example those deriving from monoamine-striazine-dicarboxylic acids carboxyalkylated, carboxylphenylates or carboxybenzylates (see DE-A-2.121.184 and 2.533.675), monohydantoins or bisidantoins, possibly benzimidazoles halogenated or parabenic acid. Carboxyalkyl groups can contain from 3 to 20 carbon atoms.

Suitable aliphatic diols are linear and branched aliphatic glycols, in particular those with 2 to 12, in particular 2 to 6 carbon atoms 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-hexandiol, <'> 1,12-dodecandiol. A suitable cycloaliphatic diol is for example 1,4-dihydr <'> oxycyclohexane. Further suitable aliphatic diols are for example 1.4-bis- (hydroxymethyl) cyclohexane, aliphatic aromatic diols such as p-xylene glycol or 2,5-dichloro-pxylene glycol, 2,2- (β-hydroxyethoxyphenyl) -propane and also polyalkylene glycols, such as diethylene glycol, triethylene glycol , polyethylene glycol or polypropylene glycol. The alkylene diols are preferably linear and contain in particular from 2 to 4 carbon atoms.

Preferred diols are alkylene diols, 1,4-dihydroxycyclohexane and 1,4-bis (hydroxymethyl) cyclohexane. particularly preferred are ethylene glycol, 1,4-butanediol and also 1,2- and 1,3-propylene glycol.

Further suitable aliphatic diols are β-hydroxyalkylated bisphenols, in particular β-hydroxyethylated, such as 2,2-bis [4 (β-hydroxyethoxy) phenyl] -propane, further bisphenols are indicated below.

A further group of suitable aliphatic diols are the heterocyclic diols described in the published German patents 1,812,003, 2,342,432, 2,342,372 and 2,453,326. Examples are: N, N'-bis- (β-hydroxyethyl) -5,5-dimethyl-hydantoin, N, N'-bis- (β-hydroxypropyl) -5,5-dimethyl-hydantoin, methylene-bis- [ N- (β-hydroxyethyl) -5-methyl-5-ethyl-hydantoin], methylen-bis- [N- (β-hydroxyethyl) -5,5-dimethylhydantoin], N, N'-bis- (β-hydroxyethyl ) -benzimidazolone, Ν, Ν'-bis- (β-hydroxyethyl- (tetrachlor) -benzimidazolone or N, N'-bis- (β-hydroxyethyl) - (tetrabromo) -benzimidazolone.

As aromatic diols one takes into consideration diphenols with one nucleus and in particular with two nuclei, which, in each aromatic nucleus, carry a hydroxyl group. The term aromatic radicals preferably refers to radicals of aromatic hydrocarbons such as for example phenylene or naphthylene. In addition to, for example, hydroquinone, resorcinol, or 1,5-2,6- and 2,7-dihydroxynaphthalene, bisphenols must be mentioned in particular, which can be represented by the following formulas:

The hydroxyl groups can be in the meta position, but in particular in the para, R 'and R "position, in these formulas, they can indicate alkyl with 1 to 6 carbon atoms, halogen such as chlorine or bromine and in particular hydrogen atoms. A can indicate a direct bond or oxygen, zol-

there-

dene, cycloalkylidene or possibly substituted alkylene.

Examples of possibly substituted alkylidenes are ethylidene, 1,1- or 2,2-propylidene, 2,2-butylidene, 1,1-isobutylidene, pentylidene, hexylidene, heptylidene, octylidene, dichloroethylidene, trichloroethylidene.

Examples of optionally substituted alkylenes are methylene, ethylene, phenylmethylene, diphenylmethylene, methylphenylmethylene. Examples of cycloalkylidenes are cyclopentylidene, cyclohexylidene, cycloeptylidene 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-hydroxyphenyl) -ethane, 1-phenyl-bis (p-hydroxyphenyl) -methane, diphenylbis (p-hydroxyphenyl) -methane, diphenyl-bis (p-hydroxyphenyl) -ethane, bis- ( 3,5-dimethyl-4-hydroxyphenyl) -sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzole, bis (3,5-dimethyl-4-hydroxyphenyl) -m-diisopropylbenzole, 2,2 -bis (3 ', 5'-dimethyl-4'-hydroxyphenyl) -propane, 1,1- or 2,2-bis (p-hydroxyphenyl) -butane, 2,2-bis (p-hydroxyphenyl) hexafluoropropane, 1 , 1-dichloro or 1,1, 1-trichloro-2,2-bis (p-hydroxyphenyl) -ethane, 1.1-bis (p-hydroxyphenyl) -cyclopentane and in particular 2.2-bis (p-hydroxyphenyl) -propane (bisphenol A) and 1,1-bis (p-hydroxyphenyl) -cyclohexane (bisphenol C).

Suitable polyesters of hydroxycarboxylic acids are, for example, polycaprolactone, polypivalolactone or the polyesters of 4-hydroxycyclohexanecarboxylic acid or 4-hydroxybenzoic acid. Furthermore, polymers are also suitable, which can mainly contain ester bonds, but also other bonds, for example polyesteramides or polyesterimides.

Polyesters with aromatic dicarboxylic acids have reached the greatest importance in particular the polyalkylene terephthalates. Therefore, molding compositions according to the invention are preferred, in which the polyester consists of at least 30 mol%, preferably at least 40 mol%, of aromatic dicarboxylic acids and for at least 30 mol%, preferably at least 40 mol%, of alkylene diols preferably with 2 to 12 carbon atoms, referred to the polyester.

In particular, in this case, the alkylene diol is linear and contains 2 to 6 carbon atoms, for example ethylene, 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 corresponding copolymers, PET and its copolymers being particularly preferred.

The term polyketones refers to plastics which are formed by the polymerization of carbon monoxide with unsaturated hydrocarbons as described for example in EP-A-0.222.454 or in EP-A-0.685.517.

Suitable compositions as described above, in which components (b) and (c) together, are present in an amount of 0.05 to 5%, in particular 0.1 to 5%, for example 0.1 to to 2%, referred to the weight of component (a).

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

In addition to components (b) and (c), the compositions according to the invention may contain further additives or co-stabilizing agents, for example the following:

1. Antioxidants

1.1 Alkylated monophenols e.g. 2,6-ditert.-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-iso-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (a-methylcyclohexyl) -4, 6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert, butyl-4-methoxymethylphenol, linear or branched nonylphenols, in the side chain as for example 2 , 6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methyl-undec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyl-heptadec -1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) -phenol and their mixtures.

1.2. Alkylthiomethylphenols, for example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-di-octylthiomethyl-6-methylphenol, 2,4-di-octylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4 -nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones e.g. 2,6-di-tert.butyl-4-methoxyphenol, 2,5-ditert.butyl-hydroquinone, 2,5-di-tert.amyl-hydroquinone, 2, 6-diphenyl-4- octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl- 4-hydroxyphenyl-stearate, bis- (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, βtocopherol, γ-tocopherol, δ-tocopherol and their mixtures (vitamin E).

1.5 Hydroxylated thiodiphenyl ethers, e.g. 2,2'-thio-bis- (6-tert.butyl-4-methylphenol), 2,2'-thiobis- (4-octylphenol), 4,4'-thio-bis- ( 6-tert.butyl-3-methylphenol), 4,4'-thio-bis- {6-tert.butyl-2-methylphenol), 4,4'-thio-bis- (3,6-di-sec- amylphenol), 4,4'-bis- (2,6-dimethyl-4-hydroxyphenyl) -disulfide.

1.6 Alkylidene bisphenols, for example, 2,2'-methylene-bis- (6-tert.butyl-4-methylphenol), 2,2'-methylene-bis- (6-tert.butyl-4-ethylphenol), 2,2'-methylen-bis- [4-methyl-6- (α-methylcyclohexyl) -phenol], 2,2'-methylen-bis- (4-methyl-6-cyclohexylphenol), 2,2'-methylene -bis- (6-nonyl-4-methylphenol), 2,2'-methylenebis- (4,6-di-tert.butylphenol), 2,2'-ethylidene-bis- (4,6-di-tert. butylphenol), 2,2'-ethylidene-bis- (6-tert.butyl-4-isobutylphenol), 2,2'-methylene-bis- [6- (amethylbenzyl) -4-nonylphenol], 2,2'- methylen-bis- [6- (α, αdimethylbenzyl) -4-nonylphenol], 4,4'-methylene-bis- (2,6-di-tert.butylphenol), 4,4'-methylene-bis- (6 -tert-butyl-2-methylphenol), 1,1-bis- (5-tert.butyl-4-hydroxy-2-methylphenyl) -butane, 2,6-di- (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-bis- (3'-tert.-butyl-4'-hydroxyphenyl) -butyrate], bis- (3 -tert-butyl-4-hydroxy-5-methylphenyl) -dicyclopentadiene , bis- [2- (3'-tert.butyl-2'-hydroxy-5'-methyl-benzyl) -6-tert.butyl-4-methyl-phenyl] -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-mercapto-butane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) -pentane.

1.7. o-, N- and S-benzyl compounds, e.g. 3,5,3 ', 5'-tetra-tert.-butyl-4,4'-dihydroxy-dibenzylether, octadecyl-4-hydroxy-3,5-dimethylbenzyl- mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris- (3,5-di-tert.-butyl-4-hydroxy-benzyl) -amine, bis- (4-tert.-butyl -3-hydroxy-2,6-dimethylbenzyl) -diotherefthalate, bis- (3, 5-di-tert. -Butyl-4-hydroxybenzyl) -sulfide, isooctyl-3, 5-di-tert. -butyl4-hydroxybenzyl-mercaptoacetate.

1.8. Hydroxybenzylated maionates, for example dioctadecyl-2,2-bis- (3,5-di-tert-butyl-2-hydroxybenzyl) -maionate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5- methylbenzyl) -malonate, di-dodecylmercaptoethyl-2,2-bis- (3,5-di-tert-butyl-4-hydroxybenzyl) -maionate, di- [4- (1,3,3-tetramethylbutyl) - phenyl] -2,2-bis- (3,5-di-tert-butyl-4-hydroxybenzyl) -maionate.

1.9. Aromatic hydroxybenzyl compounds, e.g. 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzole, 1,4-bis- (3,5- di-terzbutyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzole, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -phenol.

1.10. Triazine compounds, e.g. 2,4-bisoctylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis- (3, 5-diterz.-Butyl4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis- (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5- triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris- (3,5-diterz-butyl -4-hydroxybenzyl) -isocyanurate, 1,3,5-tris- (4-tert-butyl-3-hydroxy-2,6-di-methylbenzyl) -isocyanurate, 2,4,6-tris- (3,5 -di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris- (3,5-di-tert-butyl4-hydroxyphenylpropionyl) -hexahydro-1,3,5- triazine, 1.3.5-tris- (3,5-dicyclohexyl-4-hydroxybenzyl) -isocyanurate.

1.11. Benzylphosphonates, e.g. dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3.5-di-tert-butyl-4-hydroxybenzylphosphonate , dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzyl phosphonic acid monoethyl ester.

1.12. Acylaminophenols, for example 4-hydroxyanilide of lauric acid, 4-hydroxy-anilide of stearic acid, octyl ester of N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbamic acid.

1.13 Esters of β- (3,5-di-tert.butyl-4-hydroxyphenyl) -propionic acid with monovalent or plurivalent alcohols, such as for example with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1, 6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentylglycol, thiodethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxyethyl) -isocyanurate, Ν, Ν'-bis- (hydroxyethyl) -diamide of oxalic acid, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo

[ 2 . 2 . 2] -octane.

1.14. Esters of β- (5-tert.butyl-4- hydroxy-3-methylphenyl) -propionic acid with monovalent or plurivalent alcohols, such as for example with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1, 6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propandiol, neopentylglycol, thiodethyleneglycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxyethyl) -isocyanurate, Ν, Ν'-bis- (hydroxyamide of ethyl) oxalic acid, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexandiol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] -octane.

1.15. Esters of β- (3, S-dicyclohexylM-hydroxyphenyl) -propionic acid with monovalent or plurivalent alcohols such as for example with methanol, ethanol, octanol, octadecanol, 1,6-hexandiol, 1,9-nonandiol, ethylene glycol, 1, 2-propanediol, neopentylglycol, thiodethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxyethyl) -isocyanurate, N, N '-bis- (hydroxyethyl) -diamide of oxalic acid, 3-thiaundecanol, 3-thiapentethylhexane , 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] -

octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxy-phenylacetic acid with monovalent or plurivalent alcohols such as for example with methanol, ethanol, octanol, octadecanol, 1,6-hexandiol, 1,9-nonandiol, ethylene glycol, 1,2-propanediol, neopentylglycol, thiodethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxyethyl) -isocyanurate, Ν, Ν'-bis- (hydroxyethyl) -diamide of oxalic acid, 3-thiaundecanol, 3-thiapecanol , trimethylolpropane, 4-hydroxymethyl-1-phospha-2, 6,7-trioxabicyclo [2.2.2] -octane.

1.17. Amides of β- (3,5-di-tert.butyl-4-hydroxyphenyl) -propionic acid such as, for example, N, N'-bis- (3,5-di-tert.butyl-4-hydroxyphenylpropionyl) - hexamethylenediamine, Ν, Ν'-bis- (3,5-di-tert.butyl-4-hydroxyphenylpropionyl) -trimethylenediamine, N, N'-bis- (3,5-di-tert.butyl-4-hydroxyphenylpropionyl) - hydrazide, Ν, Ν'-bis [2 (3- [3,5-di-tert.-butyl-4-hydroxyphenyl] -propionyloxy) ethyl] oxamide (Naugard® XL-1 by Uniroyal).

1.18. Ascorbic acid (vitamin C).

1.19 Amine antioxidants: N, N'-di-isopropylp-phenylenediamine, N, N '-di-sec-butyl-p-phenylenediamine, Ν, Ν'-bis- (1,4-dimethyl-pentyl) -p-phenylenediamine , Ν, Ν'-bis- (1-ethyl-3-methyl-pentyl) -p-phenylenediamine, Ν, Ν '-bis (1-methyl-heptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p -phenylenediamine, N, N'-diphenyl-pphenylenediamine, Ν, Ν'-di- (naphthyl-2) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethyl -butyl) -N'-phenyl-p-phenylenediamine, N- (1-methyl-heptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p- toluene-sulfonamido) -diphenylamine, N, N'-dimethyl-N, N <r> -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, octyl diphenylamine, e.g. p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyryl-amino -phenol, 4-nonanoylairanino-phenol, 4-dodecanoylamino-phenol, 4-octadecanoyl-amino-phenol, di- (4-methoxyphenyl) -am mine, 2,6-di-tert-butyl-4-dimethylamino-methylphenol, 2,4'-diamino-diphenylmethane, 4,4'-diamino-diphenylmethane, Ν, Ν, Ν ', Ν'-tetramethyl-4, 4'-diamino-diphenylmethane, 1,2-di- [(2-methyl-phenyl) -amino] -ethane, 1,2-di- (phenylamino) -propane, (o-tolyl) -biguanide, di- [ 4- (1 ', 3'-dimethyl-butyl) -phenyl] aramine, N-phenyl-1-naphthylamine tert-octyl, mixture of monoalkylated and dialkylated tert-butyl / tertoctyldiphenylamines, mixture of mono- and dialkylated nonyldiphenylamines mixture of dodecyldiphenylamines mono- and di-alkylated, mixture of monoalkylated and dialkylated isopropyl / isohexyl-diphenylamines, monoalkylated and dialkylated tert-butyldiphenylamine mixtures, 2,3-dihydro-3,3-dimethyl-4H-1, 4-benzothiazine, phenothiazine, mixture of mono- and dialkylated tert-butyl / tert.octyl-phenothiazines, mono and dialkylated tert.-octylphenothiazines, N-allylphenothiazine, Ν, Ν, Ν ', Ν'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis- (2,2,6,6-tetramethyl-piperidine-4-yl) -exam tylenediamine, bis- (2,2,6,6-tetramethylpiperidin-4-yl) -sebaca to, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV light absorbing agents and photoprotective agents

2.1. 2- (2'-hydroxyphenyl) -benzotriazoles, such as, 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-tetramethyl-butyl) phenyl] -benzotriazole, 2- [3 ', 5'-di-tert.butyl-2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-terzbutyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 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, mixture of 2- (3'-tertzbutyl -2'-hydroxy-5'- (2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2' -hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 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) -benzotriazole and 2- (3'-tert-butyl-2'-hydroxy-5'- (2-isooctyloxycarbonylethyl) phenyl-benzotriazole, 2,2 '-methylen-bis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl-phenol]; transesterification product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxy-phenyl] -benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO (CH2) 3] 2 with R = 3'-tert-butyl-4-hydroxy-5-2H-benzotriazol-2-yl-phenyl, 2- [2 <1> -hydroxy-3 < ?> - (a, a-dimethylbenzyl) -5 '- (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole; 2- [2'-hydroxy-3 '- (1,1,3,3-tetramethylbutyl) -5'- (a, α-dimethylbenzyl) phenyl] -benzotriazole.

2.2. 2-hydroxybenzophenones, such as 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2 ', 4'-trihydroxy-, 2'-hydroxy-4,4'-dimethoxy derivative.

2.3. Esters of possibly substituted benzoic acids, such as, for example, 4-tert.butyl-phenylsalicylate, phenylsalicylate, octylphenyl-salicylate, dibenzoylresorcinol, bis- (4-tert.-butylbenzoyl) -resorcin, benzoylresorcinol, 2,4-ditert .butylphenyl ester 3,5-di-tert.butyl-4-hydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3,5-di-tert-butyl acid octadecyl ester -4-hydroxybenzoic, 2-methyl-4,6-di-tert-butyl-phenyl ester of 3,5-di-tert-4-hydroxybenzoic acid.

2.4. Acrylates, such as, for example, ethyl ester or isooctyl ester of a-cyano-β, β-diphenylacrylic, methyl ester of acarbometoxycinnamic acid, methyl ester or butyl ester of a-cyano ~ 3-methyl-p-methoxycinnamic acid, ester methyl acid methyl methoxy-methoxy-cinnamic acid, N- (3-carbomethoxy-3-cyanovinyl) -2-methyl-indoline.

2.5. Nickel compounds, such as, for example, complexes with nickel of 2,2'-thio-bis- [4- (1,1,3,3-tetramethylbut.yl) -phenol], such as the 1: 1 complex or the complex 1: 2, optionally with further ligands such as n-butyl-amine, triethanolamine, or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3,5-di-tert acid. -butylbenzylphosphonic as of the methyl or ethyl ester, nickel complexes of ketoxime, such as of 2-hydroxy-4-methyl-phenyl-undecylketoxime, complexes with nickel of 1-phenyl-4-lauryl-5-hydroxypyrazole possibly with further ligands .

2.6 Aromines with steric hindrance, such as, for example, bis- (2,2,6,6-tetramethyl-piperidyl) -sebacate, bis- (2,2,6,6-tetramethylpiperidyl) -succìnato, bis- (1, 2,2,6,6-pentamethylpiperidyl) -sebacate, bis- (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -sebacate, bis (1,2,2,6,6-pentamethylpiperidyl ) -ester of n-butyl-3, 5-di-tert.butyl-4-hydroxybenzyl-malonic acid, condensation product obtained from 1-hydroxyethyl-2, 2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product obtained from N, N '-bis- (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine and from 4-tert.octylamino-2,6-dichloro-1,3 , 5-s-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) -nitrilotriacetate, tetrakis- (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3, 4-butantetranoate, 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- (1,2,2,6,6-pentamethylpiperidyl) -2-nbutyl-2- (2-hydroxy-3,5-di-tert-butyl-benzyl) - but ion, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro [4.5] decan-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 product of N, N'-bis- (2,2,6,6 -tetramethyl-4-piperidyl) -hexamethylenediamine and 4-raorfolino-2,6-dichloro-1,3,5-triazine, 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, condensation product of 2-chloro-4,6-di- (4-n -butylamino-1,2,2,6,6-pentamethylpiperidyl) -1, 3,5-triazine and di 1,2-bis- (3-amino-propylamino) -ethane, 8-acetyl-3-dodecyl-7 , 7,9,9-tetramethyl-1,3,8-triaza-spiro- [4.5] -decan-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4- piperidyl) pyrrolidin-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) -pyrrolidin-2,5-dione, mixture of 4-hexadecyloxy- and 4 -stearyloxy2,2,6,6-tetramethylpiperidine, condensation product of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl ) hexamethylenediamine and 4-cyclohexylamine-2.6-dichloro-1,5-triazine, condensation product of 1,2-bis- (3-aminopropylamino) -ethane and 2,4,6-trichloro-1,3 , 5-triazine, and also 4-butylamino-2.2.6.6-tetramethylpiperidine (CAS Registration No. [136504—96—6 [); N- (2,2,6,6-tetramethyl-4-piperidyl) ndodecyl-succinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) n-dodecylsuccinimide, 2-undecyl-7, 7,9,9-tetramethyl-1-bone-3, 8-diaza-4-oxo-spiro [4.5] decane, transesterification product of 7,7,9,9-tetramethyl-2-cycloundecyl-1- bone-3, 8-diaza-4-oxospiro [4.5] -decane and epichlorohydrin, 1,1-bis (1,2,2,6,6-pentamethyl-4-piperidyl-oxycarbonyl) -2- (4- methoxyphenyl) ether, Ν, Ν '-bis-formi1-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, 4-methoxy-methylene mayionic acid diester with 1,2 , 2,6,6-pentamethyl-4-hydroxy-piperidine, poly [methylpropyl-3-oxo-4- (2,2,6,6-tetramethyl-4-piperidyl)] - siloxane, reaction product obtained from a anhydrous copolymer of maleic acid-cx-olefin and 2,2,6,6-tetramethyl-4-amino-piperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxalic acid diammides, such as, for example, 4,4'-di-octyloxy-oxanilide, 2,2'-diethoxyoxanilide, 2,2'-di-octyloxy-5,5'-di-tert.butyloxanilide, 2, 2'-di-dodecyloxy-S, 5'-di-tert.butyloxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis- (3-dimethylaminopropyl) -oxalamide, 2-ethoxy-5- tert.-butyl-2'-ethyl-oxanilide and a mixture thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert .butyloxanilide, mixtures of o- and p-methoxy- and also o- oxanilides and p-ethoxides-substituted.

2.8. 2- (2-hydroxyphenyl) -1,3,5-triazine, such as 2,4, 6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy -4-octyloxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis- (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy- 4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1 , 3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- ( 2-hydroxy-3-butyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3- octyloxy-propyloxy) 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-dodecyloxypropoxy) phenyl-4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-hexyloxy) -phenyl-4,6-diphenyl-1,3, 5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4, 6-tris [2-hydroxy-4- (3-butoxy-2 -hydroxypropoxy) phenyl-1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyienyl) -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'-diphenyl-diamide of oxalic acid, N-salicyloyl-N'-salicyloylhydrazine, N, N'-bis- (salicyloyl) -hydrazine, N, N'- bis- (3,5-di-tert.butyl-4-hydroxyphenylpropionyl) -hydrazine, 3-salicyloylamino-1, 2,4-triazole, bis- (benzylidene) -dihydrazide of oxalic acid, oxanilide, acid dihydrazide isophthalic, bis-phenylhydrazide of sebacic acid, N, N'-diacetyl-dihydrazide of adipic acid, Ν, Ν'-bis-salicyloyl-dihydrazide of oxalic acid, Ν, Ν'-bis-salicyloyl-dihydrazide of thiopropionic acid.

4. Phosphites and phosphonites, such as, for example, triphenylphosphite, diphenylalkylphosphites, phenyldyalkylphosphites, tris- (nonylphenyl) -phosphite, trilaurylphosphite, trioctadeylphosphite, distearyl-pentaerythritylphosphite, tris- (nonylphenyl) -phosphite, trilaurylphosphite, trioctadeylphosphite, distearyl-pentaerythritylphosphite -diphosphite, bis- (2,4-di-tert.butylphenyl) -pentaerythritol diphosphite, bis- (2,6-di-tertzbutyl-4-methylphenyl) -pentaerythritol diphosphite, bisisodecyloxy-pentaerythritic diphosphite, bis- (2,4-diterz -butyl-6-methylphenyl) -pentaerythritolite diphosphite, bis- (2,4,6-tri-tert-butylphenyl) -pentaerythritol diphosphite, tristearyl-sorbite-triphosphite, tetrakis- (2,4-ditert.butylphenyl) -4,4 ' -biphenylene-diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo [d, g] -1,3,2-dioxaphosphocin, 6-fluoro-2,4,8, 10-tetra-tertzbutyl-12-methyl-dibenzo [d, g] -1,3,2-dioxaphosphocin, 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. Hydroxylamines, such as N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-dithetradecylhydroxylamine, N, N-diethylhydroxyl amine, N, N -hexadecyl-N-octadecyl-hydroxylamine, N-heptadecyl-N-octadecylhydroxyl amine, N, N-dialkylhydroxylamine obtained from hydrogenated fatty tallow amines.

6. Nitrons, such as N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-octylalpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridecyl -nitrone, N-hexadecyl-alpha-heptadecyl-nitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecyl-nitrone. N-octadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-heptadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, N-derived nitrones, N-dialkyl hydroxylamines prepared from hydrogenated tallow fatty amines.

7. Thiosynergic compounds, such as for example thiodipropionic acid dilauryl ester or thiodipropionic acid distearyl ester.

8. Compounds that destroy peroxides, such as esters of β-thio-dipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyldisulfide , pentaerythritol-tetrakis (β-dodecylmercapto) -propionate.

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

10. Basic co-stabilizing agents, such as for example melamine, polyvinylpyrrolidone, dicyandiamide, triallylcyanurate, urea derivatives, hydrazine derivatives, animines, polyamides, polyurethanes, alkali metal and alkaline earth metal salts of higher fatty acids, for for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, potassium palmitate, antimony pyrocatechinate or tin pyrocatechinate.

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

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

13. Further additives, such as for example plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, spreading aids, optical whitening agents, flame protection agents, antistatic agents, propellants.

14. Benzofuranones or indolinones, as for example described in US-A-4325863, US-A-4338244, US-A-5175312, US-A-5216052, US-A-5252643, DE-A-4316611, DE- A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102, or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-2- one, 5.7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenylibenzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2 -hydroxyethoxy] -phenyl) -benzofuran-2-one], 5,7-di-tertbutyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5 , 7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxy-phenyl) -5.7-di-tert-butyl-benzofuran-2-one, 3- (3, 4-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one.

Gl. ' Costa-stabilizing agents, with the exception of the benzofuranones listed under point 14, are added, for example, in concentrations of 0.01 to 10%, referred to the total weight of the polyamide, polyester or polyketone to be stabilized.

Further preferred compositions contain, in addition to components (a), (b) and (c) still further additives, in particular phenolic antioxidants, light protection substances or / and processing stabilizers.

Particularly preferred additives are phenolic antioxidants (point 1 of the list), amines with steric hindrances (point 2.6 of the list), phosphites and phosphonites (point 4 of the list) and compounds that destroy peroxides (point 8 of the list).

Further particularly preferred additives (stabilizers) are benzofuran-2-ones, as described for example in US-A-4 .325.863, US-A-4.338.244, US-A-5.175.312, US-A-5.216. 052, US-A-5.252.643, DE-A-4.316.611, DE-A-4.316.622, DE-A-4.316.876, EP-A-0.589.839 and EP-A-0.591.102.

Examples of such benzofuran-2-ones are compounds of formula

m which

R'X1 indicates an unsubstituted or substituted aromatic, carbocyclic or heterocyclic ring system;

R'12 is hydrogen;

R'n is hydrogen, alkyl with 1 to 12 carbon atoms, cyclopentyl, cyclohexyl or chlorine;

R'13 has the meaning of R'i2 or of R'n or is

or -D-E, where

R'ie is hydrogen, alkyl with 1 to 18 carbon atoms, alkyl interrupted with oxygen or sulfur having 2 to 18 carbon atoms, dialkylaminoalkyl with a total of 3 to 16 carbon atoms, cyclopentyl, cyclohexyl, phenyl or phenyl substituted with 1 to 3 alkyl radicals having together at most 18 carbon atoms;

s is 0, 1 or 2;

the substituents R'i7 independently of each other

are hydrogen, alkyl with 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl substituted with 1 or 2 alkyl radicals having together at most 16 carbon atoms, a radical of

or, together with the nitrogen atom to which they are bound, they form a radical of piperidine or morpholine;

t indicates 1 to 18;

R'20 indicates hydrogen, alkyl with 1 to 22 carbon atoms or cycloalkyl with 5 to 12 carbon atoms;

A indicates an alkylene with 2 to 22 carbon atoms possibly interrupted with nitrogen, oxygen or sulfur;

R'ie indicates hydrogen, alkyl with 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl or benzyl substituted with 1 or 2 alkyl radicals having together at most 16 carbon atoms;

R'i9 indicates alkyl with 1 to 18 carbon atoms;

the R'2I substituents independently of each other - 45 - Ing. Barzanò & Zanardo Milano S.p.A,

are hydrogen or Ci-Cie-alkyl, both R'zi substitutes together containing 1 to 16 carbon atoms, or R'2I is phenyl or a radical of

formula -

in which s, R'ie and R'I7 have the meanings indicated above;

E is a formula radical

in which R <1> ii, R <1> 12 and R’n have the meanings indicated above; And

R'is is hydrogen, alkyl with 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, chlorine or is a

radical formula

in which R'ie and R'I7 have the meanings indicated above or R'I5 together with R'14 forms a tetramethylene radical.

Preferred are those benzofuran-2-oni, wherein R <1> 13 is hydrogen, alkyl with 1 to 12 carbon atoms, cyclopentyl, cyclohexyl, chlorine or a radical

hauls of formula

or -D-E, where s, R'ie, R'i7 / D and E have the meanings indicated above, R'ie, in particular, has the meaning of hydrogen, alkyl with 1 to 18 carbon atoms, cyclopentyl or cyclohexyl.

Furthermore, those benzofuran-2-ones are preferred, in which R'n is phenyl or is phenyl substituted with 1 or 2 alkyl radicals having together at most 12 carbon atoms; R'i2 is hydrogen; R'14 is hydrogen or alkyl with 1 to 12 carbon atoms;

R'i3 is hydrogen, alkyl with from 1 to 12 atoms of

or R'I5 together with R'I4 forms a tetramethylene radical, s, R'ie, R'I7, D and E having the meanings indicated at the beginning.

Likewise, of particular interest are those benzofuran-2-oni, in which R'13 is hydrogen, alkyl with 1 to 12 carbon atoms or is -D-E; R'12 and R '14, independently of each other, are hydrogen or alkyl with 1 to 4 carbon atoms and R'15 is alkyl with 1 to 20 carbon atoms, D and E having the indicated meanings at the beginning.

Likewise, of particular interest are, lastly, those benzofuran-2-oni, in which R'i3 is alkyl with 1 to 4 carbon atoms or -D-E; R '12 and R'i4 are hydrogen; and R'iS is alkyl with 1 to 4 carbon atoms, cyclopentyl or cyclohexyl, D being a group -C (R'2I) 2- and E being a radical of formula

the substituents R'2I being the same or different from each other and from time to time being alkyl with 1 to 4 carbon atoms; and R'X1, R'I2, R'n and R'iS having the indicated meaning.

The amount of benzofuran-2-oni further employed can vary within wide limits. For example, they can be contained in quantities of 0.0001 up to 5% by weight, preferably of 0.001 up to 2% by weight, in particular from 0.01 up to 2% by weight in the compositions according to the invention.

The introduction of components (b) and (c) and also possibly of further additives in component (a) [polyamide, polyester or polyketone] is carried out according to known methods, for example before or during forming, or also by applying the components ( b) and (c) dissolved or dispersed on component (a), possibly with subsequent evaporation of the solvent. The components (b) and (c) can be added to the products to be stabilized [component (a)] also in the form of a mother blend, which contains them for example in a concentration of 2.5 to 25% by weight.

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

Components (b) and (c) can be incorporated into component (a) to be stabilized in pure form or encapsulated in waxes, oils or polymers.

Components (b) and (c) can also be sprayed on component (a) to be stabilized. They are capable of diluting further additives, (for example the traditional additives indicated above) or their melts, so that they can be applied by spraying on the component (a) to be stabilized also together with these additives.

Particularly advantageous is the addition by spray application during the deactivation of the polymerization catalysts, using, for the spray application, for example the water vapor used for deactivation.

The polyaramides, polyesters and polyketones thus stabilized can be used in the most varied forms, for example in the form of sheets, fibers, small strips, products for molding, profiles or in the form of binders for paints, adhesives or mastics.

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

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

Components (b) and (c) are distinguished by an advantageous coloring behavior, that is, a low discoloration of the polyamides, polyesters and polyketones during processing. The present invention also relates to a process for the stabilization of a polyamide, a polyester or a polyketone against oxidative, thermal and / or light-induced degradation, characterized in that these products are introduced or applied on they 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.

Also preferred are mixtures of stabilizers, whose weight ratio of the components (i) :( ii) is between 10: 1 and 1:10, in particular between 5: 1 and 1: 5, for example between 4: 1 and 1: 2.

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

The stabilizer blends of components (i) and (ii) are referred to as "LC-Bl3⁄4nds" ("low color blends"). They are characterized by excellent storage stability, low volatility and excellent flow properties ("free flow properties"). Particularly preferred are the LC-mixtures indicated in Table 1.

Table 1:

a) Irgafos®12 corresponds to the compound of formula I. b) Irganox®1010 corresponds to the compound of formula Ile. c) Irganox®3114 corresponds to the compound of formula Ilg. e) Irganox®1098 corresponds to the compound of formula IIa. f) Irganox®1076 corresponds to the compound of formula Ilb.

The following examples further illustrate the invention. Indications in parts or percentages refer to the weight.

Example 1: Stabilization of polyamide 6.

100 parts of unstabilized polyamide 6 granulate (Ultramid® B3, BASF company) are pulverized by cryogenic grinding and

they are treated with the stabilizers indicated in table 2. The mixture is mixed with a Henschel mixer over the course of 2 minutes. Then, the powder thus obtained is dried at 80 ° C for 6 hours and is then subjected to extrusion in an extrusion device (Berstorff type) at a maximum temperature of 240 ° C and is then granulated. The obtained granulate is applied by spray on an injection molding plant at a maximum temperature of 240 ° C thus obtaining molded pieces in the form of weights having a thickness of 1.0 mm and plates having a thickness of 2.0 mm.

The pieces molded in the form of weights are aged in a circulating air oven at 140 ° C. The progress of aging is followed by determining the stress-elongation diagrams at time intervals of 1-3 days. The end point is defined as the time after which the residual elongation has decreased to 50% of its initial value. The longer this time, the better the stabilization. The results are collected in Table 2.

The slabs are aged in a circulating air oven at 80 ° C for 1500 hours. The yellowing index (YI) of these plates is determined according to ASTM D 1925-70. Low YI values indicate little color change. High YI values indicate a strong color change of the specimen. The smaller the color change, the more active the stabilizer mixture is. The results are collected in Table 2.

Table 2:

a) Irgafos®168 (Ciba Geigy) indicates tris (2,4-di-tert.-butylphenyl) -phosphite.

b) Irganox®1098 (Ciba Geigy) indicates N, N'-bis (3,5-ditert.-butyl-4-hydroxyphenylpropionyl) -hexamethylenediamine (compound of formula IIa).

C) Irgafos®12 (Ciba-Geigy) indicates 2,2 ', 2 "-nitrilo- [triethyl-tris (3,3', 5,5'-tetra-tert.-butyl-1,1'-biphenyl- 2,2'-diyl) -phosphite]; Chemical Abstract "Registry" number: 80410-33-9 and represents the compound of formula I.

From the results of Table 2 it can be seen that the mixture of stabilizers according to the invention (example 1a) is considerably more effective compared to the known mixture of stabilized agents (example Ib).

Claims (18)

CLAIMS 1. Composition, containing a) a polyamide, a polyester or a polyketone subject to oxidative, thermal or light-induced degradation, b) the phosphite of formula I m which Ri represents Ci-C «-alkyl, n stands for 1, 2, 3 or 4, 0 0 X represents methylene, -CH2-CH2-C yl-Y-or-CH2-C1-O-CH2-CH2-Y is oxygen or -NH-; And when n stands for 1, X represents - Y being bonded to R2 and Rz is C1-C25-alkyl; And when n is 2, X represents being bonded to R2, and R2 indicates C2-C12-alkylene, C4-Ci2-alkylene interrupted by oxygen or by sulfur; or, when Y indicates -NH-, R2 also represents a direct bond; and when n is 3, X represents methylene or the ethylene group being bonded to R 2, when n is 4, X represents Y being bonded to R2, and R2 denoting C4-C0 ~ alkantetrayl. 2. Composition according to claim 1 containing, as component (c) at least one compound of formula II, wherein, when n indicates 1, R2 represents C1-C20-alkyl. 3. Composition according to claim 1, containing, as component (c) at least one compound of formula II, wherein when n is 2, R2 represents C2-C8-alkylene, C4-C8-alkylene interrupted by oxygen or by sulfur; or when Y represents -NH-, R2 also represents a direct bond; And when n is 4, R2 represents C4-C8-alkantetrayl. 4. Composition according to claim 1, containing, as component (c) at least one compound of formula II, wherein Ri represents methyl or tert.-butyl, n stands for 1, 2 or 4, 0 X represents - CH2— CH2— C I— Y—, Y indicates oxygen or -NH-; And when n stands for 1, R2 represents C 4-C 8-alkyl; And when n is 2, R2 represents C4-C6-alkylene or C4-C6-alkylene interrupted by oxygen; And when n is 4, R2 represents C4-C6-alkantetrayl. 5. Composition according to claim 1, wherein component (c) indicates at least one compound of formula IIa, IIb, Ile or IId 6. Composition according to claim 5, wherein component (c) represents a compound of formula IIa, IIb or Ile. 7. Composition according to claim 1, wherein the polyamide is polyamide 6, polyamide 6.6, polyamide 11 or polyamide 12, or a copolymer thereof. 8. Composition according to claim 1, wherein the polyester is a PET, PETG or PBT or a copolymer thereof. 9. Composition according to claim 1, wherein the components (b) and (c) together are present in the amount of 0.05 to 5% based on the weight of the component (a). 10. Composition according to claim 1, wherein the weight ratio of the components (b) :( c) is comprised between 10: 1 and 1: 10i 11. Composition according to claim 1, containing, in addition to components (b) and (c) further additives. Composition according to claim 11, containing, as further phenolic antioxidant additives, light protection agents or / and processing stabilizers. 13. Composition according to claim 11, containing, as a further additive, at least one compound of the benzofuran-2-oni 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 oxidative, thermal and / or light-induced degradation. 15. Use according to claim 14 as processing stabilizers. 16. Process for the stabilization of a polyamide, a polyester or a polyketone against oxidative, thermal and / or light-induced degradation, characterized by the fact that phosphite of formula I and at least one compound of formula II, as defined in claim 1. 17. Blend of stabilizers containing (i) the phosphite of formula I and (ii) at least one compound of formula II as defined in claim 1. 18. Mixture of stabilizers according to claim 17, wherein the weight ratio of the components (i) :( ii) is comprised between 10: 1 and 1:10.