DE19712788A1 - Stabilization of polyamide, polyester and polyketone - Google Patents

Description

The present invention relates to compositions containing a polyamide, polyester or polyketone, a certain organic phosphite (Irgafos®12, Ciba-Geigy) and a ste hindered phenol, the use of the same for stabilizing polyamide, poly ester or polyketone against oxidative, thermal and / or light-induced degradation, and a process for stabilizing these plastics.

From US Pat. No. 4,360,617 it is known that stabilizer mixtures are contained tend to be symmetrical triaryl phosphites and certain phenolic antioxidants well suited, certain organic materials such as polyurethane, poly acrylonitrile, polyamide-12 or polystyrene before oxidative, thermal or light-induced Protect degradation. The preferred symmetrical triaryl phosphite is tris (2,4-di-tert butylphenyl) phosphite (Irgafos®168, Ciba-Geigy).

These known stabilizer mixtures can be found in polyamides, polyesters and polyketones do not meet all requirements. It is known that such a stabilizer mix the initial color as well as the color development of the polyamide during the oven reduce aging and the deterioration of the mechanical properties of the poly Reduce amids during oven aging and exposure. As a disadvantage of this Stabilisa It is often observed that these phosphites tend to bloom.

In U.S. Patents 4,318,845 and 4,374,219, alkanolamine esters of cycli 1,1′-biphenyl-2,2′-diyl and alkylidene-1,1′-biphenyl-2,2′-diyl phosphites as stabilizers gates for organic polymers and lubricating oils, especially as processing stabilizers ren for polyolefins, elastomers, polyesters and polycarbonates disclosed.

It has now been found that a stabilizer mixture containing a very specific one Phosphite selected from U.S. Patents 4,318,845 and 4,374,219 with a very specific group of sterically hindered phenols are suitable as stabilizers for polyamides, polyesters or polyketones. The buttocks stabilized in this way Lyamides, polyesters or polyketones have improved properties with regard to oxidati  ven, thermal and / or light-induced degradation. The invention Phosphite not bloomed.

The present invention therefore relates to compositions containing

• a) a polyamide subjected to oxidative, thermal or light-induced degradation, Polyester or polyketone,
• b) the phosphite of the formula I. and
• c) at least one compound of formula II wherein
  R₁ represents C₁-C₄-alkyl,
  n means 1, 2, 3 or 4, represents
  Y is oxygen or -NH-; and
  if n means 1 represents, wherein Y is bound to R₂, and
  R₂ is C₁-C₂₅ alkyl; and
  if n is 2, represents, wherein Y is bound to R₂, and
  R₂ C₂-C₁₂ alkylene, C₄-C₁₂ alkylene interrupted by oxygen or sulfur;
  or, if Y is -NH-, R₂ additionally represents a direct bond; and
  if n is 3, represents, wherein the ethylene group is bonded to R₂, and is; and
  if n means 4 represents, wherein Y is bound to R₂, and
  R₂ means C₄-C₁₀ alkane tetrayl.

Alkyl with up to 25 carbon atoms means a branched or unbranched radical such as 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-ethyl hexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylun decyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, Heptadecyl, octadecyl, eicosyl or docosyl. A preferred meaning of R₁ is methyl and tert-butyl. A particularly preferred meaning of R₂ is C₁-C₂₀ alkyl, in particular C₁-C₁₈ alkyl, e.g. B. C₄-C₁₈ alkyl. A particularly preferred meaning of R₂ is C₈-C₁₈ alkyl, especially C₁₄-C₁₈ alkyl, e.g. B. C₁₈ alkyl.

C₂-C₁₂ alkylene means a branched or unbranched radical such as Ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octa methylene, decamethylene or dodecamethylene. A preferred meaning of R₂ is for example C₂-C₁₀ alkylene, especially C₂-C₈ alkylene. A particularly preferred meaning device of R₂ is, for example, C₄-C₈ alkylene, especially C₄-C₆ alkylene, for. B. Hexamethy len.

C₄-C₁₂ alkylene interrupted by oxygen or sulfur can be one or more times be interrupted and means for example -CH₂-O-CH₂CH₂-O-CH₂-, -CH₂- (O-CH₂CH₂-) ₂O-CH₂-, -CH₂- (O-CH₂CH₂-) ₃O-CH₂-, -CH₂- (O-CH₂CH₂-) ₄O-CH₂-, -CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂- or -CH₂CH₂-S-CH₂CH₂-. A preferred meaning of R₂ is, for example, interrupted by oxygen or sulfur C₄-C₁₀ alkylene, in particular special interrupted by oxygen or sulfur C₄-C₈ alkylene, for. B. by Sauer Substance or sulfur interrupted C unterbrochen-C₆ alkylene. A particularly preferred meaning of R₂ is -CH₂CH₂-O-CH₂CH₂-O-CH₂CH₂- or -CH₂CH₂-S-CH₂CH₂-.

Alkanetetrayl with 4 to 10 carbon atoms means, for example

Pentaerythrityl is preferred.

Component (c) can also be mixtures of different steric ge hindered phenols of formula II act.

Of interest are compositions containing as component (c) at least one A compound of formula II, wherein when n is 1, R₂ is C₁-C₂₀ alkyl.

Compositions containing as component (c) are preferred at least one compound of the formula II in which
if n is 2,
R₂ C₂-C₈ alkylene, C₄-C₈ alkylene interrupted by oxygen or sulfur; or, if Y represents -NH-, R₂ additionally represents a direct bond; and
if n means 4
R₂ represents C₄-C₈-alkane tetrayl.

Also preferred are compositions containing as component (c) at least one compound of the formula II in which
R₁ represents methyl or tert-butyl,
n means 1, 2 or 4,

represents
Y represents oxygen or -NH-; and
if n means 1
R₂ represents C₁₄-C₁₈ alkyl; and
if n is 2,
R₂ is C₄-C₆ alkylene, or C₄-C₆ alkylene interrupted by oxygen; and
if n means 4
R₂ represents C₄-C₆-alkane tetrayl.

Also of interest are compositions containing at least component (c) tens a compound of formula I, wherein the compound of formula I is a compound of Formula IIa to IIh

means.

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

Compositions containing as component (c) are preferred Binding of formula I, wherein the compound of formula I is a compound of formula IIa, IIb, IIc or IId, in particular a compound of formula IIa, IIb or IIc, e.g. B. a verb of formula IIa.

Component (b) of the composition according to the invention, or the phosphite Formula I is known and its production in the aforementioned US patent 4,318,845 and 4,374,219 in Example 4. This phosphite can be in different NEN modifications occur, such as in the following US patent specification ten are disclosed. US 5,276,076 describes a solid amorphous form of the phosphite Formula I. US 5,334,739 discloses the α-crystalline form of the phosphite of formula I. US  5,326,802 describes the β-crystalline form and US 5,321,031 the γ-crystalline form of Phosphites of formula I. The phosphite of formula I is commercially available under the protected Na men Irgafos®12 (Ciba-Geigy) available.

Component (c) of the composition according to the invention, or the compounds Formula II are known and some are commercially available. Possible manufacturing process Ren for the compounds of formula II are, for example, in the US patents 3,330,859 or 3,960,928.

Among polyamides are aliphatic and aromatic polyamides or copolyamides, which are diamines and dicarboxylic acids and / or aminocarboxylic acids or their corresponding derived lactams to understand. Suitable polyamides are, for example: PA 6, PA 11, PA 12, PA 46, PA 6.6, PA 6.9, PA 6.10 or PA 6.12, PA 10.12, PA 12.12 as well also amorphous polyamides of the Trogamid PA 6-3-T and Grilamid TR 55 types mentioned type are generally known and commercially available.

Of interest are compositions containing as component (a) polyamide 6, poly amide 6.6, polyamide 11 or polyamide 12 or copolymers thereof, in particular polyamide 6 or polyamide 6.6 or elastomer-modified polyamide 6 or polyamide 6.6 with polypropylene.

Polyesters can be homo- or mixed polyesters, which are made from aliphatic, cycloaliphatic or aromatic dicarboxylic acids and diols or hydroxycarboxylic acid ren are built.

The aliphatic dicarboxylic acids can have 2 to 40 carbon atoms, the cycloaliphatic dicar bonic acids 6 to 10 carbon atoms, the aromatic dicarboxylic acids 8 to 14 carbon atoms, the ali phatic hydroxy carboxylic acids 2 to 12 carbon atoms and aromatic such as cycloalipha tables contain hydroxycarboxylic acids 7 to 14 carbon atoms.

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

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

It is also possible that the polyester with small amounts, for. B. 0.1 to 3 mol%, bezo to the existing dicarboxylic acids, more than difunctional monomers (e.g. Penta erythritol, trimellitic acid, 1,3,5-tri (hydroxyphenyl) benzene, 2,4-dihydroxybenzoic acid or 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane) are branched.

In the case of polyesters composed of at least 2 monomers, these can be randomly distributed or it can be can be block copolymers.

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

As aliphatic dicarboxylic acids are those with 2 to 40 carbon atoms in question, for. B. oxalic acid right, malonic acid, dimethylmalonic acid, succinic acid, pimelic acid, adipic acid, trimethyl adipic acid, sebacic acid, azelaic acid and dimer acids (dimerization products from un saturated aliphatic carboxylic acids such as oleic acid), alkylated malonic and succinic acid ren such as octadecyl succinic acid.

Possible cycloaliphatic dicarboxylic acids are: 1,3-cyclobutanedicarboxylic acid, 1,3- Cyclopentanedicarboxylic acid, 1,3- and 1,4-cyclohexanedicarboxylic acid, 1,3- and 1,4- (dicarbo xylmethyl) cyclohexane, 4,4'-dicyclohexyldicarboxylic acid.

Suitable aromatic dicarboxylic acids are: in particular terephthalate acid, isophthalic acid, o-phthalic acid, and 1,3-, 1,4-, 2,6- or 2,7-naphthalenedicarbon acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 4,4'-benzophenondi carboxylic acid, 1,1,3-trimethyl-5-carboxyl-3- (p-carboxylphenyl) indane, 4,4'-diphenyletherdi carboxylic acid, bis-p- (carboxylphenyl) methane or bis-p- (carboxylphenyl) -ethane.

Aromatic dicarboxylic acids are preferred, among them especially terephthalic acid. Isophthalic acid and 2,6-naphthalenedicarboxylic acid.  

Other suitable dicarboxylic acids are those containing -CO-NH groups; They are in DE-A 24 14 349 described. Also dicarboxylic acids, the N-heterocyclic rings ent hold, are suitable, for. B. those that differ from carboxylalkylated, carboxylphenylated or carboxybenzylated monoamine-s-triazinedicarboxylic acids (cf. DE-A 21 21 184 and 25 33 675), mono- or bishydantoins, optionally halogenated benzimidazoles or derive parabanic acid. The carboxyalkyl groups can have 3 to 20 carbon atoms contain.

Suitable aliphatic diols are the linear and branched aliphatic glycols, be especially those with 2 to 12, especially 2 to 6 carbon atoms in the molecule, e.g. E.g .: ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 1,3-, 2,3- or 1,4-butanediol, pentyl glycol, neo pentylglycol, 1,6-hexanediol, 1,12-dodecanediol. A suitable cycloaliphatic diol is e.g. B. 1,4-dihydroxycyclohexane. Other suitable aliphatic diols are e.g. B. 1,4-bis (hydroxymethyl) cyclohexane, aromatic aliphatic diols such as p-xylylene glycol or 2,5- Dichloro-p-xylylene glycol, 2,2- (ß-hydroxyethoxyphenyl) propane and polyoxyalkylene glycols such as diethylene glycol, triethylene glycol, polyethylene glycol or polypropylene glycol. The alky Lendiols are preferably linear and contain in particular 2 to 4 carbon atoms.

Preferred diols are the alkylene diols, 1,4-dihydroxycyclohexane and 1,4-bis (hydroxy methyl) cyclohexane. Ethylene glycol, 1,4-butanediol and 1,2- and 1,3-propylene glycol.

Other suitable aliphatic diols are the β-hydroxyalkylated, especially β-hydroxy ethylated bisphenols such as 2,2-bis [4 ′ - (β-hydroxyethoxy) phenyl] propane. Other bisphenols are mentioned later.

Another group of suitable aliphatic diols are those in the German Offen documents 18 12 003, 23 42 432, 23 42 372 and 24 53 326 heterocyc diols. 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], methylene-bis- [N- (P-hydroxyethyl) -5,5-dimethylhydantoin], N, N'-bis- (β-hydroxy ethyl) benzimidazolone, N, N'-bis (β-hydroxyethyl) - (tetrachlor) benzimidazolone or N, N'-bis- (β-hydroxyethyl) - (tetrabromo) benzimidazolone.  

Mononuclear diphenols are suitable as aromatic diols, and especially bicernuels ge, which carry a hydroxyl group on each aromatic nucleus. Under become aromatic preferably hydrocarbon aromatic radicals such as. B. phenylene or naphthylene ver stood. In addition to e.g. As hydroquinone, resorcinol or 1,5-, 2,6- and 2,7-dihydroxynaphthalene The bisphenols, which are represented by the following formulas, should be mentioned in particular can:

The hydroxyl groups can be in the m position, but especially in the p position, R ′ and R '' can in these formulas alkyl with 1 to 6 carbon atoms, halogen such as chlorine or bromine and in particular mean hydrogen atoms. A can stand for a direct bond, or

possibly substituted alkylidene, cycloalkylidene or alkylene.

Examples of optionally substituted alkylidene are: ethylidene, 1,1- or 2,2-propyli den, 2,2-butylidene, 1,1-isobutylidene, pentylidene, hexylidene, heptylidene, octylidene, dichloro ethylidene, trichloroethylidene.

Examples of optionally substituted alkylene are methylene, ethylene, phenylmethylene, Diphenylmethylene, methylphenylmethylene. Examples of cycloalkylidene are cyclopentyli the, cyclohexylidene, cycloheptylidene and cyclooctylidene.

Examples of bisphenols are: bis (p-hydroxyphenyl) ether or thioether, bis (p-hydroxy phenyl) sulfone, bis (p-hydroxyphenyl) methane, bis (4-hydroxyphenyl) -2,2'-biphenyl, phenyl hydroquinone, 1,2-bis (p-hydroxyphenyl) ethane, 1-phenyl-bis (p-hydroxyphenyl) methane, di phenyl-bis (p-hydroxyphenyl) methane, diphenyl-bis (p-hydroxyphenyl) -ethane, bis (3,5-di methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene, Bis (3,5-dimethyl-4-hydroxyphenyl) -m-diisopropylbenzene, 2,2-bis (3 ', 5'-dimethyl-4'-hydroxy phenyl) propane, 1,1- or 2,2-bis (p-hydroxyphenyl) butane, 2,2-bis (p-hydroxyphenyl) hexa fluoropropane, 1,1-dichloro- or 1,1,1-trichloro-2,2-bis (p-hydroxyphenyl) ethane, 1,1-bis (p hydroxyphenyl) cyclopentane and especially 2,2-bis (p-hydroxyphenyl) propane (bisphenol-A) and 1,1-bis (p-hydroxyphenyl) cyclohexane (bisphenol-C).

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

Furthermore, there are also polymers which are predominantly ester bonds, but also other bonds can contain suitable, such as. B. polyester amides or polyester imides.

Polyesters with aromatic dicarboxylic acids have gained the greatest importance, especially especially the polyalkylene terephthalates. Formmas according to the invention are therefore preferred sen, in which the polyester from at least 30 mol%, preferably at least 40 mol%, aro Matic dicarboxylic acids and at least 30 mol%, preferably at least 40 mol%, is composed of alkylene diols with preferably 2 to 12 carbon atoms, based on the poly ester.

In particular, the alkylene diol is linear in this case and contains 2 to 6 carbon atoms, such as. B. Ethylene, tri, tetra or hexamethylene glycol and the aromatic dicarboxylic acid tereph thalic and / or isophthalic acid.

Particularly suitable polyesters are PET, PETG (glycol-modified polyethylene tereph thalat) or PBT and corresponding copolymers, with PET and its copolymers spe are preferred.

Polyketones are understood to mean plastics that are produced by polymerizing carbon monoxide with unsaturated hydrocarbons, such as in EP-A-0 222 454 or EP-A-0 685 517.

Compositions as described above, in which the compo elements (b) and (c) together in an amount of 0.05 to 5%, in particular 0.1 to 5%, for example 0.1 to 2%, based on the weight of component (a).

Compositions are also preferred in which the weight ratio of the components (b) :( c) 10: 1 to 1:10, in particular 5: 1 to 1: 5, for example 4: 1 to 1: 2.

In addition to components (b) and (c), the combinations according to the invention contain additional additives or costabilizers, such as fol areas:  

1. Antioxidants

• 1.1. Alkylated monophenols, e.g. B. 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphe nol, 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- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxy methylphenol, linear or branched in the side chain nonylphenols such. B. 2,6-Di-no nyl-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'-methyl-tridec-1'-yl) phenol and mixture against it.
• 1.2. Alkylthiomethylphenols, e.g. B. 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4-di-octylthio methyl-6-methylphenol, 2,4-di-octylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-no nylphenol.
• 1.3. Hydroquinones and alkylated hydroquinones, e.g. B. 2,6-di-tert-butyl-4-methoxyphenol, 2,5- Di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxy anisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adi pat.
• 1.4. Tocopherols, e.g. B. α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and Mi. of it (vitamin E).
• 1.5. Hydroxylated thiodiphenyl ethers, e.g. B. 2,2'-thio-bis (6-tert-butyl-4-methylphenol), 2,2'- Thio-bis (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-hydroxy phenyl) disulfide.
• 1.6. Alkylidene bisphenols, e.g. B. 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 methylene-bis (4-methyl-6-cyclohexylphenol), 2,2-methylene-bis (6-nonyl-4-methylphenol),  2,2′-methylene-bis (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- (α-methylbenzyl) -4-nonyl phenol], 2,2'-methylene-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-hy droxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphe nol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy- 2-methyl-phenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hy droxyphenyl) 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-ph-enyl] 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-dodecylmercapto-b-utan, 1,1,5,5-tetra- (5- tert-butyl-4-hydroxy-2-methylphenyl) pentane.
• 1.7. O-, N- and S-benzyl compounds, e.g. B. 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-butylbenzyl-mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-bu tyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetate.
• 1.8. Hydroxybenzylated malonates, e.g. B. Dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybene zyl) malonate, di-octadecyl 2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, di-dodecyl mercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, di- [4- (1,1, 3,3-tetramethyl butyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.
• 1.9. Hydroxybenzyl aromatics, e.g. B. 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trime thylbenzene, 1,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene-, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.
• 1.10. Triazine compounds, e.g. B. 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) - 1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-tr-iazine, 2-oc tylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazi-n, 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) isocya nurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di  tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-ter-t-butyl-4-hydroxyphenyl propionyl) hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydoxybenzyl) isocyanurate.
• 1.11. Benzylphosphonates, e.g. B. Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, Di ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxy benzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, Ca salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.
• 1.12. Acylaminophenols, e.g. B. 4-hydroxy-lauric anilide, 4-hydroxystearic anilide, N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamic acid octyl ester.
• 1.13. Ester of (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyvalent against alcohols, such as B. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-He xandiol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hy droxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, Trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- [2.2.2] octane.
• 1.14. Esters of (3- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with one or more quality alcohols, such as B. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1.6- Hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol col, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis- (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, Trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- [2.2.2] octane.
• 1.15. Esters of β- (3.5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyvalent against alcohols, such as B. 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 (hydroxy ethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trime thylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- [2.2.2] octane.  
• 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyvalent Al alcohols such as B. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonane diol, 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.
• 1.17. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, such as e.g. B. N, N'-bis (3,5-di tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydro xyphenylpropionyl) trimethylene diamide, N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) - hydrazide, N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] o-xamide (Nau gard®XL-1 from Uniroyal).
• 1.18. Ascorbic acid (vitamin C).
• 1.19. Amine antioxidants, such as. B. N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec butyl-p-phenylenediamine, N, N'-bis (1,4-dimethyl-pentyl) -p-phenylenediamine, N, '- bis (1-ethyl-3- methyl-pentyl) -p-phenylenediamine, N, N'-bis (1-methyl-heptyl) -p-phenylenediamine, N, N'-dicyc lohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di- (2-naphthyl) -p-pheny lendiamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethyl-butyl) -N'-phenyl-p-phe nylenediamine, N- (1-methyl-heptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p- phenylenediamine, 4- (p-toluenesulfonamido) diphenylamine, N, '- dimethyl-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 tes diphenylamine, e.g. B. p, p-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylami no-phenol, 4-nonanoylamino-phenol, 4-dodecanoylamino-phenol, 4-octadecanoylamino- phenol, di- (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylamino-methyl-phenol, 2,4- Diamino-diphenylmethane, 4,4'-diamino-diphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diami no-diphenylmethane, 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-naph thylamine, mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, Ge mix of mono- and dialkylated nonyldiphenylamines, mixture of mono- and dialky gelled dodecyldiphenylamines, mixture of mono- and dialkylated isopropyl / isohexyl-di  phenylamines, mixtures of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihy dro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixture of mono- and dialkylated tert-butyl / tert-octyl-phenothiazines, mixture of mono- and dialkylated tert-octyl-pheno thiazines, N-allylphenothiazine, N, N, N ′, N′-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis- (2,2,6,6- tetramethyl-piperidin-4-yl-hexamethylenediamine, bis (2,2,6,6-tetramethylpiperidin-4-yl) seba cat, 2,2,6,6-tetramethypiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV absorber and light stabilizer

• 2.1. 2- (2'-hydroxyphenyl) benzotriazoles, such as. B. 2- (2'-Hydroxy-5'-methylphenyl) benzotri azole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert- Butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3', 5'-di-tert-butyl- 2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chloro-benzotriazole, 2- (3'-sec-butyl-5 'Tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy xy-4'-octoxyphenyl) benzotriazole, 2- (3', 5'-di-tert-amyl-2'-hydroxyphenyl ) -benzotriazole, 2- (3 ′, 5′-bis (α, α-dimethylbenzyl) -2′-hydroxyphenyl) -benzotriazole, 2- (3′-tert-butyl-2′-hydroxy-5′- (2 -octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-Butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - ( 2-methoxy carbonylethyl) phenyl) benzotriazole , 2- (3'-tert-Butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-Butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] -2-hydroxyphen-yl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hy droxy-5 ' - (2-isooctyloxycarbonylethyl) phenyl-benzotriazole, 2,2'-methylene-bis [4- (1,1,3,3-tetra methylbutyl) -6-benzotriazol-2-yl-phenol], transesterification product of 2- [ 3-tert-butyl-5- (2-methoxycarbonylethyl) -2-hydroxyphenyl] benzotriazole with polyethylene glycol 300, with R = 3'-tert-butyl-4-hydroxy-5-2H-benzotriazol-2-yl phenyl; 2- [2′-hydroxy-3 ′ - (α, α-dimethylbenzyl) -5- (1,1,3,3-tetramethylbutyl) phenyl] benzotri azole; 2- [2′-Hydroxy-3 ′ - (1,1,3,3-tetramethylbutyl) -5 ′ - (α, α-dimethylbenzyl) phenyl] benzotri azole.
• 2.2.2 Hydroxybenzophenones, such as. B. the 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 optionally substituted benzoic acids, such as. B. 4-tert-butylphenylsali cylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) -re sorcinol, 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-butylphe- nyl ester.
• 2.4. Acrylates such as B. α-cyan-β, β-diphenylacrylate or isooctyl ester, α-car methyl bomethoxy cinnamate, methyl α-cyano-β-methyl p-methoxy cinnamate or -butyl ester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester, N- (β-carbomethoxy-β-cya novinyl) -2-methyl-indoline.
• 2.5. Nickel compounds such as B. Nickel complexes of 2,2'-thio-bis [4- (1,1,3,3-tetramethyl butyl) phenols], such as the 1: 1 or the 1: 2 complex, optionally with additional ligan such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithio carbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as from methyl or ethyl esters, nickel complexes from ketoximes, such as from 2-hydro xy-4-methyl-phenyl-undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyra zols, optionally with additional ligands.
• 2.6. Sterically hindered amines, e.g. B. bis (2,2,6,6-tetramethyl-piperidin-4-yl) sebacate, bis- (2,2,6,6-tetramethyl-piperidin-4-yl) succinate, bis (1,2,2,6,6-pentamethyl-piperidin-4-yl) seba cat, bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, n-butyl-3,5-di-tert-butyl-4-hy droxybenzyl-malonic acid bis (1,2,2,6,6-pentamethylpiperidyl) ester, condensation product from 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products from N, N'-bis (2,2,6,6-tetramethyl-4-piperidy) hexamethy lendiamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris (2,2,6,6-tetramethyl-4-piperi dyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetraoate, 1,1- (1,2- Ethanediyl) -bis (3,3,5,5-tetramethyl-piperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4- Stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2- hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6-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) hexamethylene diamine and 4-morpholino-2,6-dichloro-1,3,5-tri azine, condensation product from 2-chloro-4,6-di- (4-n-butylamino-2,2,6,6-tetramethylpipen dyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, condensation product from 2- Chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-t-riazine and 1,2-bis (3-ami nopropylamino) -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-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, mixture of 4-hexadecyloxy and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, condensation product from N, N′-bis (2,2,6,6-tetra methyl-4-piperidyl) hexamethylene diamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, Condensation product from 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-tri azine and 4-butylamino-2,2,6,6-tetramethyl-piperidine (CAS Reg. No. [136504-96-6]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-pipendyl) - n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4,5] decane, - Reaction 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-pipendyloxycarbonyl) -2- (4th methoxyphenyl) ethene, N, N'-bis-formyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethy lendiamine, diester of 4-methoxy-methylene-malonic acid with 1,2,2,6,6-pentamethyl-4-hy doxy-piperidine, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, Reak tion product from maleic anhydride-α-olefin copolymer and 2,2,6,6-tetramethyl-4-amino piperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.
• 2.7. Oxalic acid diamides, such as. B. 4,4-di-octyloxy-oxanilide, 2,2-diethoxy-oxanilide, 2,2'-di-oc tyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'- ethyl oxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2-ethylox anilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl-oxanilide, mixtures of o- and p-methoxy and of o- and p-ethoxy-di-substituted oxanilides.
• 2.8. 2- (2-hydroxyphenyl) -1,3,5-triazines such as e.g. B. 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-tri-azine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyl oxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4- methyl-phenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6- bis (2,4-dimethylphenyl) - 1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2-  [2-Hydroxy-4- (2-hydroxy-3-butyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-tri azine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-d-imethylphenyl) - 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-tri azine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3- butoxy-2-hydroxy-propoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) - 6-phenyl-1,3,5-triazine, 2- (2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] phenyl- 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.
• 3. Metal deactivators, such as. B. N, N'-Diphenyloxalsäurediamid, N-salicylal-N'-salicyloyl hydrazine, N, N′-bis (salicyloyl) hydrazine, N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalic acid dihydrazide, oxanilide, iso phthalic acid dihydrazide, sebacic acid bis-phenylhydrazide, N, N'-diacetyl-adipic acid dihy drazid, N, N'-bis-salicyloyl-oxalic acid dihydrazide, N, N'-bis-salicyloyl-thiopropionic acid dihy drazid.
• 4. Phosphites and phosphonites, such as. B. triphenyl phosphite, diphenylalkyl phosphites, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, diste aryl-pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol-di phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis- (2,6-di-tert-butyl-4-methyl) phenyl) pentaerythritol diphosphite, bis-isodecyloxy-pentaerythritol diphosphite, bis (2,4-di-tert-bu tyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-ri-tert-butylphenyl) pentaerythritol di phosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene-di phosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxap-phosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphosphocin, bis (2,4-di tert-butyl-6-methylphenyl) methylphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethylphos phit, 2-ethylhexyl- (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) -ph-osphite.
• 5. Hydroxylamines such as B. N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctyl hydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhy hydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-Hep tadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine from hydrogenated tallow fatty amines.  
• 6. Nitrons such as B. N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-octyl-al pha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridecyl-nitrone, N-He xadecyl-alpha-pentadecyl-nitron, N-octadecyl-alpha-heptadecyl-nitron, N-hexadecyl-alpha heptadecyl-nitrone, N-octadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-heptadecyl-ni tron, N-octadecyl-alpha-hexadecyl-nitrone, nitrones derived from N, N-dialkylhydroxylamines made from hydrogenated tallow fatty amines.
• 7. Thiosynergists such as B. thiodipropionic acid di-laurylester or thiodipropionic acid di stearyl ester.
• 8. Peroxide-destroying compounds, such as. B. esters of β-thio-dipropionic acid, for example as the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt des 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, penta erythritol tetrakis (β-dodecylmerapto) propionate.
• 9. polyamide stabilizers, such as. B. copper salts in combination with iodides and / or Phos phosphorus compounds and salts of divalent manganese.
• 10. Basic co-stabilizers, such as. B. melamine, polyvinylpyrrolidone, dicyandiamide, tri allyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, Alkali and alkaline earth salts of higher fatty acids, e.g. Ca stearate, Zn stearate, Mg Behenate, magnesium stearate, sodium ricinoleate, K-palmitate, antimony pyrocatecholate or zinc pyraca techinat.
• 11. Nucleating agents, such as. B. inorganic substances such. B. talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of preferably earth alkali metals; organic compounds such as mono- or polycarboxylic acids and their Salts such as B. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such. B. ionic copolymers ("Iono mere ").  
• 12. Fillers and reinforcing agents, such as. As calcium carbonate, silicates, glass fibers, glass balls, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, Wood flour and flours or fibers of other natural products, synthetic fibers.
• 13. Other additives, such as B. plasticizers, lubricants, emulsifiers, pigments, rheolo giadditives, catalysts, flow control agents, optical brighteners, flame retardants, anti static, propellant.
• 14. Benzofuranones or indolinones, such as. B. in US 4,325,863; US 4,338,244; U.S. 5,175,312, U.S. 5,216,052; US 5,252,643; DE-A 43 16 611; DE-A 43 16 622; DE-A 43 16 876; EP-A-0589839 or EP-A-059 1102, or 3- [4- (2-acetoxy ethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxy ethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-di methylphenyl) -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.

The costabilizers, with the exception of the benzofuranones listed under point 14, who for example in concentrations of 0.01 to 10%, based on the total weight of the stabilizing polyamide, polyester or polyketone added.

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

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

Additional additives (stabilizers) which are also particularly preferred are benzofuran-2- one such as See, for example, 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 43 16 611, DE-A 43 16 622, DE-A 43 16 876, EP-A-0 589 839 and EP-A-0 591102.  

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

wherein
R'₁₁ represents an unsubstituted or substituted carbocyclic or heterocyclic aromatic ring system;
R'₁₂ is hydrogen;
R'₁₄ is hydrogen, alkyl of 1 to 12 carbon atoms, cyclopentyl, cyclohexyl or chlorine;
R'₁₃ has the meaning of R'₁₂ or R'₁₄ or a radical of the formula

is what
R'₁₆ hydrogen, alkyl having 1 to 18 carbon atoms, alkyl interrupted by oxygen or sulfur having 2 to 18 carbon atoms, dialkylaminoalkyl having a total of 3 to 16 carbon atoms, cyclopentyl, cyclohexyl, phenyl or substituted by 1 to 3 alkyl radicals with a total of at most 18 carbon atoms Is phenyl;
s is 0, 1 or 2;
the substituents R'₁₇ independently of one another hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl substituted by 1 or 2 alkyl radicals having a maximum of 16 carbon atoms, a radical of the formula

are or together with the nitrogen atom to which they are attached form a piperidine or morpholine residue;
t 1 to 18;
R′₂₀ are hydrogen, alkyl having 1 to 22 carbon atoms or cycloalkyl having 5 to 12 carbon atoms;
A is an alkylene with 2 to 22 carbon atoms which may be interrupted by nitrogen, oxygen or sulfur;
R′₁₈ is hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl or benzyl substituted by 1 or 2 alkyl radicals having a total of at most 16 carbon atoms;
R'₁₉ represents alkyl of 1 to 18 carbon atoms;
D is -O-, -S-, -SO-, -SO₂- or -C (R'₂₁) ₂-;
the substituents R'₂₁ are independently hydrogen or C₁-C₁₆ alkyl, the two R'₂₁ together containing 1 to 16 carbon atoms, or R'₂₁ phenyl or egg nen radical of the formula

is where s, R'₁₆ and R'₁₇ have the meanings given above
E is a remainder of the formula

wherein R'₁₁, R'₁₂ and R'₁₄ have the meanings given above; and
R'₁₅ hydrogen, alkyl having 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, chlorine or
a rest of the formula

is where R'₁₆ and R'₁₇  have the meanings given above, or R'₁₅ together with R'₁₄ a tetra forms methylene radical.

Preferred are those benzofuran-2-ones in which R'₁₃ is hydrogen, alkyl with 1 to 12 Koh lenstoffatomen, cyclopentyl, cyclohexyl, chlorine or a radical of the formula

or -DE is where s, R'₁₆, R ' ₁₇₁ D and E have the meanings given above, R'₁₆ in particular has the meaning of hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl or cyclohexyl.

Also preferred are those benzofuran-2-ones in which R'₁₁ is phenyl or phenyl substituted by 1 or 2 alkyl radicals with a maximum of 12 carbon atoms; R'₁₂ is hydrogen; R'₁₄ is hydrogen or alkyl of 1 to 12 carbon atoms;
R′₁₃ is hydrogen, alkyl having 1 to 12 carbon atoms,

or -D-E; R′₁₅ is hydrogen, alkyl having 1 to 20 carbon atoms,

is or R'₁₅ together with R'₁₄ one Tetramethylene forms, where s, R'₁₆, R'₁₇, D and E the meaning given at the beginning have.

Also of particular interest are those benzofuran-2-ones in which R'₁₃ water is fabric, alkyl of 1 to 12 carbon atoms, or -D-E; R'₁₂ and R'₁₄ independently of one another which are hydrogen or alkyl of 1 to 4 carbon atoms; and R'₁₅ alkyl having 1 to 20 Is carbon atoms, where D and E have the meanings given above.

Also of particular interest are finally those benzofuran-2-ones in which R'₁₃ is alkyl having 1 to 4 carbon atoms or -DE; R'₁₂ and R'₁₄ are hydrogen;
and R'₁₅ alkyl having 1 to 4 carbon atoms, cyclopentyl or cyclohexyl, where D is a group -C (R'₂₁) ₂- and E is a radical of the formula

is, wherein the substituents R'₂₁ are the same or different and each alkyl with 1 are to 4 carbon atoms, and R'₁₁, R'₁₂, R'₁₄ and R'₁₅ have the meaning ha ben.

The amount of additional benzofuran-2-ones used can vary within wide limits vary. For example, they can be 0.0001 to 5, preferably 0.001 to 2, in particular especially 0.01 to 2 wt .-%, contained in the compositions according to the invention be.

The incorporation of components (b) and (c) and optionally further additives into the Component (a) [polyamide, polyester or polyketone] is carried out by known methods, for example before or during shaping or by applying the loosened or dispersed components (a) and (b) on component (a), optionally under subsequent evaporation of the solvent. Components (b) and (c) can also in the form of a masterbatch, for example in a concentration of 2.5 to Contains 25 wt .-%, the materials to be stabilized [component (a)] are added.

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

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

Components (b) and (c) can also be applied to component (a) to be stabilized be sprayed. You are able to get other additives (e.g. the ones listed above conventional additives) or their melts, so that they also together can be sprayed onto the component (a) to be stabilized with these additives.  

The addition by spraying during the deactivation of the bottom is particularly advantageous polymerization catalysts, z. B. the steam used for deactivation to Ver spray can be used.

The polyamides, polyesters and polyketones stabilized in this way can be in various forms be applied, e.g. B. as films, fibers, tapes, molding compounds, profiles or as a bin detergent for paints, adhesives or putties.

Components (b) and (c) are particularly suitable as processing stabilizers (heat stabilizers). For this purpose, they will be beneficial before or during processing added to 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 stabilizer ren, in particular processing stabilizers (thermal stabilizers) for polyamides, poly esters or polyketones against oxidative, thermal or light-induced degradation.

Components (b) and (c) are distinguished by an advantageous color behavior, i.e. H. ge wrinkle discoloration of polyamides, polyesters and polyketones during processing.

The present invention also relates to a method for stabilizing a polyamide, Polyesters or polyketons against oxidative, thermal and / or light-induced degradation, characterized in that the phosphite of formula I and at least one Incorporates or applies compound of formula II.

The present invention also relates to a stabilizer mixture comprising (i) the Phos phit of the formula I and (ii) at least one compound of the formula II.

Stabilizer mixtures in which the weight ratio of the components are also preferred ten (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 formula II for use as stabilizers, the Stabilization methods and the stabilizer mixture are the same as for the Compositions with a polyamide, polyester or polyketone are described.  

The stabilizer mixtures of components (i) and (ii) are called "LC blends" ("Low Color Blends "). They are characterized by excellent storage stability, ge wrestling volatility and excellent free flowing properties. The LC blends listed in Table 1 are particularly preferred.

Table 1

a) Irganox®12 corresponds to the compound of formula I.
b) Irganox®1010 corresponds to the compound of formula IIc.
c) Irganox®3114 corresponds to the compound of formula IIg.
d) Irganox®1098 corresponds to the compound of formula IIa.
e) Irganox®1076 corresponds to the compound of formula IIb.

The following examples further illustrate the invention. Parts or percentages relate to weight.  

example 1 Stabilization of polyamide 6

100 parts of unstabilized polyamide 6 granules (Ultramid®B3, BASF) are through Cryogenic grinding pulverized and ver with the stabilizers specified in Table 2 puts. The mixture is mixed with a Henschel mixer for 2 minutes. Subsequently the powder thus obtained is dried at 80 ° C for 6 hours and then extruded in an extruder (Berstorff type) at a maximum of 240 ° C. and then granulated liert. The granules obtained are 1.0 mm on an injection molding machine at a maximum of 240 ° C thick dumbbells and 2.0 mm thick plates sprayed.

The dumbbells are aged in a forced air oven at 140 ° C. The progression of aging is ver by determining the force-strain diagrams at intervals of 1-3 days follows. The end point is defined as the time after which the residual elongation reaches 50% of its start catch value has dropped. The longer the time, the better the stabilization. The Resul Tates are summarized in Table 2.

The panels are aged in a forced air oven at 80 ° C for 1500 hours. From the The yellowness index (Y1) is determined according to ASTM D 1925-70. Low YI Values mean little discoloration, high YI values strong discoloration of the pattern. Ever the less discoloration, the more effective the stabilizer mixture. The results are in Ta belle 2 summarized.  

Table 2

a) Irgafos®168 (Ciba-Geigy) means tris (2,4-di-tert-butylphenyl) phosphite.
b) Irganox®1098 (Ciba-Geigy) means N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamine (compound of the formula IIa).

c) Irgafos®12 (Ciba-Geigy) means 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 in Table 2 it can be seen that the stabilizer gene according to the invention mixed (Example 1c) compared to the known stabilizer mixture (Example 1b) clearly is more effective.

Claims (18)

1. Composition containing

• a) a polyamide, polyester or polyketone subjected to oxidative, thermal or light-induced degradation,
• b) the phosphite of the formula I. and
• c) at least one compound of formula II wherein
  R₁ represents C₁-C₄-alkyl,
  n means 1, 2, 3 or 4, represents
  Y is oxygen or -NH-; and
  if n means 1 represents, wherein Y is bound to R₂, and
  R₂ is C₁-C₂₅ alkyl; and
  if n is 2, represents, wherein Y is bound to R₂, and
  R₂ C₂-C₁₂ alkylene, C₄-C₁₂ alkylene interrupted by oxygen or sulfur; or, if Y is -NH-, R₂ additionally represents a direct bond; and
  if n is 3, represents, wherein the ethylene group is bonded to R₂, and is; and
  if n means 4 represents, wherein Y is bound to R₂, and
  R₂ means C₄-C₁₀ alkane tetrayl.

2. Composition according to claim 1, containing at least component (c) a compound of formula II, wherein when n is 1, R₂ is C₁-C₂₀ alkyl.   3. Composition according to claim 1, containing as component (c) at least one compound of formula II, wherein
if n is 2,
R₂ C₂-C₈ alkylene, C₄-C₈ alkylene interrupted by oxygen or sulfur; or, if Y represents -NH-, R₂ additionally represents a direct bond; and
if n means 4
R₂ represents C₄-C₈-alkane tetrayl. 4. Composition according to claim 1, containing as component (c) at least one compound of formula II, wherein
R₁ represents methyl or tert-butyl,
n means 1, 2 or 4, represents
Y represents oxygen or -NH-; and
if n means 1
R₂ represents C₁₄-C₁₈ alkyl; and
if n is 2,
R₂ is C₄-C₆ alkylene, or C₄-C₆ alkylene interrupted by oxygen; and
if n means 4
R₂ represents C₄-C₆-alkane tetrayl. 5. The composition according to claim 1, wherein component (c) at least one compound of formula IIa, IIb, IIc or IId means. 6. The composition according to claim 5, wherein component (c) is a compound of Formula IIa, IIb or IIc represents. 7. The composition of claim 1, wherein the polyamide is a polyamide 6, polyamide 6.6, polyamide 11 or polyamide 12 or a copolymer thereof. 8. The composition of claim 1, wherein the polyester is a PET, PETG or PBT or a copolymer thereof. 9. The composition of claim 1, wherein components (b) and (c) together present in an amount of 0.05 to 5% based on the weight of component (a). 10. The composition of claim 1, wherein the weight ratio of the components ten (b) :( c) is 10: 1 to 1:10. 11. The composition according to claim 1, comprising in addition to components (b) and (c) additional additives. 12. The composition according to claim 11, containing phenolic as further additives Antioxidants, light stabilizers and / or processing stabilizers. 13. The composition according to claim 11, containing at least one further additive a compound of the benzofuran-2-one type.   14. Use of the phosphite of the formula I and at least one compound of For mel 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. A method for stabilizing a polyamide, polyester or polyketone against oxide tive, thermal and / or light-induced degradation, characterized in that one these the phosphite of the formula I and at least one compound of the formula II, as described in Claim 1 are defined, incorporated or applied to this. 17. Stabilizer mixture containing (i) the phosphite of the formula I and (ii) at least one A compound of formula II as defined in claim 1. 18. The stabilizer mixture according to claim 17, wherein the weight ratio of the compo nenten (i) :( ii) is 10: 1 to 1:10.