NL1010729C2 - Stabilization of polyamide, polyester and polyacetal. - Google Patents

Description

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Stabilization of polyamide, polyester and polvacetal

The present invention relates to compositions comprising a polyamide, a polyester or a polyketone, to a specific phenolic antioxidant, to their use for stabilizing polyamides, polyesters or polyacetals against oxidative, thermal and / or light-induced degradation as well as a method of stabilizing these plastic materials.

It is known from US Pat. Nos. 3691131 and 3860558 that polyamides can be stabilized with phenolic antioxidants in the presence of metal hypophosphites, such as potassium hypophosphite or sodium hypophosphite, and of copper salts of organic acids,

In polyamides, polyesters or polyacetals, these known stabilizer mixtures cannot meet all the requirements imposed on them. It is known that such stabilizer blends reduce the initial color as well as the color development of the polyamide during oven aging and further reduce the deterioration of the mechanical properties of the polyamide during oven aging and upon exposure to light.

It has now been found that a specific phenolic antioxidant. which is selected from U.S. Pat. Nos. 3691131 and 3860558 is particularly suitable as a stabilizer for polyamides, polyesters or polyacetals in the absence of metal hypophosphites and copper salts of organic acids. The polyamides stabilized in this way. Polyesters or polyacetals have improved properties with respect to oxidative, thermal or / and light-induced degradation.

Accordingly, this invention relates to compositions. comprising 30 a) a polyamide, polyester or polyacetal subject to oxidative, thermal or light-induced degradation and 1010729 *% 2

b) the compound of the formula I.

H, C H C CH3 Η30 = λ, η ΐι / Κ ^ 0Η3

HO — Λ — CH2 — CH —C —NH - (CH2) 6 —NH-C —CH2-CH2 — C λ — OH

f 5 CH 3 CH 3 (I).

with the proviso that if component (a) is a polyamide, then the composition will not contain any metal hypophosphite and no copper salt of an organic acid, and provided that as component (a) is a polyester-polyether copolymer, then the composition will not contain an organotin compound contains.

Component (b) of the new composition, or the compound of the formula I, is known and has Chem.Abstr. registration number [37042-77-6]. The preparation of the compound of the formula I is described in GB-A-1251840, example 1, p. 5.

It is understood that polyamides include aliphatic and aromatic polyamides or copolyamides derived from diamines and dicarboxylic acids and / or from amino carboxylic acids or their corresponding lactams. Suitable polyamides are for example: PA-6, PA-11, PA-12, PA-46, PA-6,6, PA-4,6, PA-6,9, PA-6,10 or PA-6,12 PA-10,12, PA-12,12 and also amorphous polyamides of the type Trogamid PA 6-3-T and! Grilamid TR 55. Polyamides of the type mentioned are generally known and are commercially available.

Interesting compositions are those in which component (a) is polyamide-6, polyamide-6,6, polyamide-4,6, polyamide-11 or polyamide-12 or copolymers thereof, in particular polyamide-6 or polyamide-6, 6 or modified with an elastomer; Polyamide-6 or polyamide-6,6 mixed with polypropylene.

The polyesters used can be homo- or copolyesters consisting of aliphatic, cycloaliphatic or aromatic dicarboxylic acids and diols or hydroxycarboxylic acids.

The aliphatic dicarboxylic acids can have 2 to 40 carbon atoms, the cycloaliphatic dicarboxylic acids 6 to 10 carbon atoms, the aromatic dicarboxylic acids 8 to 14 carbon atoms, the aliphatic hydroxycarboxylic acids 2 to 12 carbon atoms and the aromatic, e.g. cycloaliphatic, hydroxycarboxylic acids contain 7 to 14 carbon atoms.

The aliphatic diols can contain from 2 to 12 carbon atoms, the cyclo-1010729 3 aliphatic diols from 5 to 8 carbon atoms and the aromatic diols from 6 to 16 carbon atoms.

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

The polyesters can also be branched with small amounts, e.g. 0.1 to 3 mol *, based on the dicarboxylic acids present, of more than difunctional monomers (eg pentaerythritol, trimellitic acid, 1,3,5-tri (hydroxyphenyl) benzene. 2,4-dihydroxybenzoic acid or 2- (4-hydroxyphenyl) -2- ( 2,4-dihydroxyphenyl) propane).

Polyesters consisting of at least 2 monomers can have a statistical distribution or they can be block copolymers.

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

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

Suitable cycloaliphatic dicarboxylic acids are: 1,3-cyclobutane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid. 1,3- and 1,4-cyclohexane dicarboxylic acid, 1,3- and 1,4- (dicarboxylmethyl) cyclohexane. 4,4'-dicyclohexyl dicarboxylic acid.

Suitable aromatic dicarboxylic acids are: in particular terephthalic acid, isophthalic acid, o-phthalic acid and also 1,3-, 1,4-, 2,6- or 2,7-na phthalene dicarboxylic acid, 4,4'-di phenyldi carboxylic acid, 4, 4'-diphenylsulfonodicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, 1,1,3-trimethyl-5-carboxyl-3- (p-carboxylphenyl) indane, 4,4'-di phenyl ether dicarboxylic acid, bis-p- (car-30 boxylphenyl) methane or bis-p- (carboxylphenyl) ethane.

The aromatic dicarboxylic acids are preferred, especially terephthalic acid thereof. isophthalic acid and 2,6-naphthalenedicarboxylic acid.

Other suitable dicarboxylic acids are those containing -CO-NH groups 35: these are described in DE-A-2414349. Dicarboxylic acids containing N-heterocyclic rings are also suitable, for example those derived from carboxylalkylated, carboxylphenylated or carboxybenzylated monoamine-s-triazine dicarboxylic acids (see DE-A-1010729 4 2121184 and 2533675), mono or bishydantoins, optionally halogenated benzim parabanoic acid. In this context, the carboxyalkyl groups can contain from 3 to 20 carbon atoms.

Suitable aliphatic diols are the linear and branched aliphatic glycols, in particular those containing 2 to 12, preferably 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-butane diol, pentyl glycol, neopentyl glycol. 1,6-hexanediol, 1,12-dodecane-1 diol. A suitable cycloaliphatic diol is e.g. 1,4-dihydroxycyclohexane. Other suitable aliphatic diols include, for example, 1,4-bis (hydroxymethyl) cyclohexane, aromatic-aliphatic diols such as p-xylylene glycol or 2.5-dichloro-p-xylylene glycol, 2.2 - (?-Hydroxyethoxy - = phenyl) propane and polyoxyalkylene glycols, such as ethylene glycol, triethylene glycol, polyethylene glycol or polypropylene glycol. The alkylene diols are preferably linear and preferably contain 2 to 4 carbon atoms.

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

Other suitable aliphatic diols are the SS-hydroxy-alkylated, especially --hydroxyethylated bisphenols, such as 2,2-bis- [4 ”(β-hydroxyethoxy) phenylpropane. Other bisphenols are mentioned later i.

Another group of suitable aliphatic diols is that of the heterocyclic diols described in DE-A-1812003. DE-A- | 2342432, DE-A-2342372 and DE-A-2453326. Examples are: N, N'-bis (0-hydroxyethyl) -5,5-dimethylhydantoin, N.N'-bis (/ 3-hydroxypropyl) -5.5- | dimethylhydantoin, methylene bis [N- (β-hydroxyethyl) -5-methyl-5-ethyl-hydantoin], methylene bis [N - (/ 3-hydroxyethyl) -5,5-dimethylhydantoin], 'NN * bis (/? -hydroxyethyl) benzimidazolone, N.N'-bis (/? - hydroxyethyl) - (tetrachloro) benzimidazolone or N.N'-bis (/? - hydroxyethyl Ktetrabromo) benzimidazolone.

Suitable aromatic diols are diphenol and with a core and. in particular, di-cores with two cores containing a hydroxyl group on each aromatic core. The term aromatic preferably refers to hydrocarbon-aromatic residues, for example phenylene or naphthylene. Besides e.g. hydroquinone, resocrcinol or 1,5-, 1010729 5 2,6- and 2,7-dihydroxynaphthalene, in particular the bisphenols should be mentioned, which can be represented by the following formulas: 5 R 'R' R 'R' ” φ ~ φ "3 & -Φ R” R ”R” R ”10“ φ-Φ-φ "R” R ”15 20 R” R "25 R” R "R 'R' 30 HQyK. [ΛΛ A / 4 ^ oh ψ ΛΛρ- ψ R "R" 35 1010729 6: The hydroxyl groups can be in the m position. in particular, in the p-position. R 'and R "in these formulas can mean alkyl of 1 to 6 carbon atoms, halogen, such as chlorine or bromine, and preferably hydrogen atoms. A can be a direct bond or oxygen, sulfur, -S0-, -SO2- C = O, -P (O) (C 1 -C 20 alkyl) -, unsubstituted or substituted alkylidene, cycloalkylidene or alkylene.

Examples of unsubstituted or substituted alkylidene 10 are: ethylidene. 1,1- or 2,2-propylidene, 2,2-butylidene, 1,1-iso-butylidene, pentylidene, hexylidene. heptyliden. octylidene, dichloroethylidene, trichlorethylidene.

Examples of unsubstituted or substituted alkylene are methylene, ethylene, phenylmethylone. diphenylmethyl one, methylphenyl-15 methyl one. Examples of cycloalkylidene are cyclopentylidene, cyclohexylidene, cycloheptylidene and cyclooctylidene.

Examples of bisphenols are: bis (p-hydroxyphenyl) ether or bis (p-hydroxyphenyl) thioether, bis (p-hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, bis (4-hydroxyphenyl) -2,2 ' -biphenyl. phenylhydrochi. 20 nun. 1,2-bis (p-hydroxyphenyl) ethane. 1-phenyl-bis (p-hydroxyphenyl) -methane, diphenyl-bis (p-hydroxyphenyl) methane, diphenyl-bis (p-hydroxyphenyl) ethane, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone. bis (3,5-di-methyl-4-hydroxyphenyl) -p-diisopropyl benzene, bis (3,5-dimethyl-4-hydroxy phenyl) -m-diisopropyl benzene. 2,2-bis (3 ', 5'-dimethyl-4'-hydroxy-phenyl) 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-hydroxycyclohexane carboxylic acid or 4-hydroxybenzoic acid.

Also suitable are polymers which mainly contain ester bonds, but also other bonds, such as, for example, polyester amides or polyester imides.

Polyesters containing aromatic dicarboxylic acids have become extremely important, especially the polyalkylene terephthalates. Accordingly, those molding products according to the invention are preferred, wherein the polyester consists of at least 30 mol *, preferably at least 40 mol * aromatic dicarboxylic acids and at least 30 mol *, preferably at least 40 mol * alkylene diols which are preferably contain 2 to 12 carbon atoms based on the polyester.

In this case, the alkylene diol is preferably linear and contains 2 to 6 carbon atoms. such as ethylene, tr, tetra or hexamethylene glycol. and the aromatic dicarboxylic acid is terephthalic and / or isophthalic acid.

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

Polyacetals are, for example, homopolymers or copolymers of paraformaldehyde, such as in particular polyoxymethylene (POM). and those polyoxymethylenes, which are comonomers. such as ethylene oxide. and 15 polyacetals modified with thermoplastic polyurethanes. acrylates or MBS.

Useful compositions are those as described above, wherein component (b) is present in an amount of 0.01 to 1 *. preferably 0.02 to 0.8 *. for example 0.03 to 0.6 *. based on the weight of component (a).

In addition to components (a) and (b), the new compositions may contain additional additives or costabilizers, such as the following: 1. Antioxidants 1.1 Alkylated monophenols. for example 2,6-di-tert-butyl-4-methyl phenol. 2-tert-butyl-4,6-dimethyl phenol, 2,6-di-tert-butyl-4-ethyl phenol. 2,6-di-tert-butyl-4-n-butylphenol. 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol. 2- (α-methylcyclohexyl) -4,6-dimethyl phenol, 2,6-dioctadecyl-4-methylphenol. 2,4,6-tricyclohexylphenol. 2,6-di-tert-butyl-4-methoxymethylphenol, linear or side chain branched nonylphenol and, such as e.g. 2,6-Dinonyl-4-methyl-phenol, 2,4-dimethyl-6- (1 '-methylundec-Γ-yDphenol, 2,4-dimethyl-6- (1-methylheptadec-Γ-yl) phenol. 2.4- dimethyl-6- (Γ-methyl tri dec-Γ-yl) -phenol and mixtures thereof.

1.2 Alkylthiomethylphenols. for example 2,4-dioctylthiomethyl-6-35 tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol. 2,4-dioctylthiomethyl-6-ethyl phenol. 2,6-didodecylthiomethyl-4-nonylphenol.

1.3 Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol. 2,5-di-tert-butylhydroquinone, 2,5-1010729 8 di-tert-amylhydrochi non, 2,6-diphenyl-4-octadecyloxyphenol. 2.6-di-tert-! butyl hydrochi non. 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.

5 1.4 Tocopherol and. for example, α-tocopherol. /? - tocopherol. / -toco ferol. d-tocopherol and mixtures thereof (vitamin E).

. 1.5 Hydroxylated thiodiphenyl ethers, for example 2.2'-thio-bis (6-tert-butyl-4-methyl phenol), 2,2'-thiobis (4-octyl phenol). 4.4''s thi obis (6-tert-butyl-3-methyl phenol). 4.4'-thiobis (6-tert-butyl-2-. 10 methyl phenol). 4.4'-thiobis (3,6-di-sec-amyl phenol), 4.4'-bis (2,6-di methyl -4-hydroxyphenyl) di sulfide.

1.6 Alkvlidene bisphenols. for example, 2,2'-methylenebis (6-tert-butyl-4-methylphenol). 2.2'-methylene bis (6-tert-butyl-4-ethyl phenol), 2,2'-methylene bis [4-methyl-6- (α-methylcyclohexyl) phenol]. 2,2'-15 methylene bis (4-methyl-6-cyclohexyl phenol), 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-butyl phenol), 2,2'-ethylidene bis (6-tert-butyl -4-isobutyl phenol), 2,2'-methylenebis [6- (o -methylbenzyl) -4-nonylphenol]. 2,2'-methylenebis [6- (a, a-dimethylbenzyl) -4-nonylphenol], 4,4'-20methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-) 2-methylphenol). 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol. 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane ethylene-25-glycol-bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bi s (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bi s [2 - (3'-tert-butyl -2 '-hydroxy-5'-methyl benzyl) -6-tert-butyl -4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane 2,2-bis (3,5-di-tert-f-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methyl-phenyl) -4-n- dodecyl mercaptobutane. 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.

1.7 0-. N- and S-benzyl compounds, for example 3.5.3'5'-t-t-t-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethyl benzyl mercaptoacetate, tridecyl-4-hydroxy -3,5-di-tert-butyl-35 benzyl mercaptoacetate, tri s (3,5-di-tert-butyl-4-hydroxybenzyl) amine, - bis (4-tert-butyl-3-hydroxy-2,6-dimethyl benzyl) ) dithoterephthalate. bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl -4-hydroxybenzyl mercaptoacetate.

1010729 9 1.8 Hydroxybenzylated malonates. for example dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate. dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate. didodecyl mercaptoethyl-2.2-b i s (3.5 - di -1ert - buty 1 - 4 - hydroxybenzy 1) ma 1 ona at. d i [4 - (1.1.3.3 -1-tetra-5-methyl-butyl) phenyl] -2.2-bis (3.5-di-tert-butyl-4-hydroxybenzyl) malonate.

1.9 Aromatic hvdroxvbenzvl connection points. for example, 1,3,5-tri s (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene. 1,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3.5,6-tetramethylbenzene.

2,4,6-tri s (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.

10 1.10 Triazine compounds. for example 2,4-bis (octyl mercapto) - 6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine. 2-octylmercap-to-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine. 2-octyl mercapto-4,6-bis (3,5-di-tert-butyl -4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tri s (3,5-di-tert- butyl-4-hydroxyphenoxy) -1,2,3-triazine.

1,3,5-tri s (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate. 1,3,5-tris- (4-tert-butyl-3-hydroxy-2,6-dimethyl benzyl) 1socyanurate, 2,4,6-tri s- (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3 , 5-triazine, 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine.

1,3,5-tri s (3,5-dicyclohexyl-4-hydroxybenzyl) socyanurate.

20 1.11 Benzyl phosphonates. for example, dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di-octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate. di-octadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate. the Ca salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

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

1.13 Esters of g- (3,5-di-tert-butyl-4-hydroxyphenyl) prionic acid with mono- or polyhydric alcohols, such as e.g. with methanol, ethanol.

N-octanol, iso-octanol, octadecanol. 1,6-hexanediol. 1,9-nonanediol. ethylene glycol. 1,2-propanediol. neopentyl glycol. thiodiethylene glycol. diethylene glycol, triethylene glycol. pentaerythritol. tris (hydroxyethyl) isocyanurate. N.N'-bis (hydroxyethyl) oxalic acid diamide. 3-thiaundecanol. 3-thiapentadecanol. trimethylhexanediol. trimethylolpropane. 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.14 Esters of g- (5-tert-butyl-4-hydroxyl-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, such as e.g. with methanol, ethanol, n-octanol, iso-octanol. octadecanol, 1,6-hexanediol, 1,9-1010729 nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thioethylene glycol, diethylene glycol. triethylene glycol. pentaerythritol. tri s (hydroxyethyl) socyanurate, N, N'-bi s (hydroxyethyl) oxalic acid diamine, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri-5 methylol propane, 4-hydroxymethyl-1-phospha-2,6, 7-trioxabicyclo [2.2.2] octane.

- 1.15 Esters of fl- (3,5-dicvclohexyl-4-hydroxylphenylpropionic acid with mono- or polyhydric alcohols, such as, for example, with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol , neopentyl glycol, thiodiethylene glycol, diethylene glycol triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N.N'-bis (hydroxyethyl) oxalic acid diamide. 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, 4-trimethylol-1-propanol. -phospha-2,6,7-tri oxabi cyclo [2.2.2] octane.

1.16 Esters of 3,5-di-tert-butyl-4-hydroxydenflacetic acid with mono or polyhydric alcohols, such as e.g. with methanol, ethanol, octanol. octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol. 1,2-propanediol, neopentyl glycol, thiodiethylene glycol. diethylene glycol, triethylene glycol. pentaerythritol. tris (hydroxyethyl) isocyanurolate, N.N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol. trimethylolpropane, 4-hydroxy methyl -1-phospha-2,6,7-trioxabi cyclo [2.2.2] octane.

1.17 Amides of [alpha] - (3.5- di-tert-butyl-4-hydroxyphenylpropionic acid), such as, for example, N.N'-bi s (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine. N, N 'bis (3,5-di-tert-butyl -4-hydroxyphenylpropionyl) trimethylenediamine, N. N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropynyl) hydrazide NN * bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (Naugard® XL-1, supplied by Uniroyal).

1.18 Ascorbic Acid (Vitamin C).

30 1.19 Amine antioxidants. such as e.g. N.N'-diisopropyl-p-phenylenediamine, N.N'-di-sec-butyl-p-phenylenediamine, N.N'-bisd. 4-dimethyl-pentyl) -p-phenylenediamine, N. N'-bis (1-ethyl-3-methyl-pentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N N'-dicyclohexyl-p-phenylenediamine, N'-diphenyl-p-phenylenediamine, N'-35 bis (2-naphthyl) -p-phenylenediamine. N-isopropyl-N'-phenyl-p-phenylene-. diamine. N- (1,3-dimethyl-butyl) -N'-phenyl-p-phenylenediamine, N- (1- methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine 4- (p-toluenesulfonamido) diphenylamine, N, N'-dimethyl - 1010729 11 N, N-di-sec-butyl-p-phenylenediamine, di-phenylamine. N-allyl diphenylamine, 4-isopropyl phenyl amine. N-phenyl-1-naphthylamine. N- (4-tert-octylphenyl) -1-naphthylamine. N-phenyl-2-naphthylamine, octylated diphenylamine. e.g. p.p'-di-tert-octyldiphenylamine. 4-n-butylaminophenol. 4-5 butyrylaminophenol. 4-nonanoylaminophenol. 4-dodecanoylaminophenol. 4- octadecanoylaminophenol. di (4-methoxyphenyl) amine. 2,6-di-tert-butyl-4-dimethyl amino methyl phenol. 2.4'-diami nodiphenylmethane, 4.4'-diamino di phenylmethane. N, N, N ". N'-tetramethyl-4,4'-diamidodi phenylmethane, 1,2-di [(2-methylphenyl) amino] ethane. 1,2-di (phenylamino) propane, (o-tolyl) - 10 biguanide. di [4- (1,3'-dimethylbutyl) phenyl] amine. tert-octylated N-phenyl-1-naphthylamine, mixture of mono- and di-alkylated tert-butyl / tert-octyldiphenylamines. mixture of mono and di-alkylated nonyldiphenylamines. mixture of mono and di-alkylated dodecyl diphenylamines, mixture of mono and di-alkylated isopropyl / iso-hexyldiphenylene amines, mixture of mono and di-alkylated tert-butyldi phenylamines, 2,3-di hydro-3,3- dimethyl-4H-1,4-benzothiazine.

phenothiazine, mixture of mono- and di-alkylated tert-butyl / tert-octylphenothiazines, mixture of mono- and di-alkylated tert-octyl-phenothiazines, NaLylphenothiazine, NNN'.N'-tetraphenyl-1,4 diamino-20-but-2-ene, N, N-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine. bi s (2.2.6.6-tetramethylpi peri di ne-4-yl) sebacate. 2.2.6,6-tetramethylpi peri di ne-4-one, 2,2,6,6-tetramethylpi peri di ne-4-ol.

2. UV absorbers and light stabilizers. 2.1 2- (2'-Hydroxylphenyl benzyl triazoles. Such as, for example, 2- (2'-25 hydroxy-5'-methylphenyl) benzotriazole, 2- (3'5'-di-tert-butyl) -2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole. 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzo triazole. 2 - (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl 5-chlorobenzo-triazole, 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-Ca.a-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3' -tert-butyl-2'-hydroxy-5 '- (2-octyl-oxycarbonylethyl) phenyl) -5-chlorobenzotriazole. 2- (3'-tert-butyl-5 '- [2-35 (2-ethylhexyloxy) carbonyl ethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2 '-hydroxy-5' - (2-methoxycarbonylethyl) -phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- ( 3'-tert-butyl-2'-hydroxy-1010729 '12 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. 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-5 methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benztri azol-2-y1 phenol], the transesterification product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonyl-ethyl) -2'-hydroxyphenyl] benzotriazole with polyethylene glycol 300; [R-CH2CH2-C00 -CH2CH2] 2- with R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzazazaz-2-ylphenyl, 2- [2'-hydroxy-3 '- (a, a-dimethylbenzyl) ) -5 '- (1,1,3,3-10 tetramethyl butyl) phenyl] benzotriazole, 2- [2'-hydroxy-3' - (1,1,3,3-tetramethyl butyl) -5 '- (aa-dimethylbenzyl) phenyl] benzotriazole.

3 2.2 2-hydroxylbenzophenones. such as, for example, the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, ~ 4,2 ', 4'-trihydroxy- and 2'-hydroxy- 4,4'-dimethoxy derivative.

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

2.4 Acrylic ions, such as, for example, α-cyano -β.β-ύ \ phenyl acrylic acid-ethyl ester resp. isooctyl ester, α-carbomethoxy-cinnamic acid-methyl ester, α-cyano- / - methyl-p-methoxy-cinnamic acid-methyl ester or -butyl ester, α-carbomethoxy-p-methoxy-cinnamic acid methyl ester and N - (?-carbomethoxy - / --cyanovinyl) -2-methylindoline.

2.5 Nickel compounds, such as, for example, nickel complexes of 2,2'-thiobis [4- (11,3-tetramethylbutyl) phenol], such as the 1: 1 or 1: 2 complex, optionally with additional ligands, such as n- butylamine, tri-ethanol amine or N-cyclohexyldiethanolamine, nickel dibutyldithio-; carbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, such as of 2-hydroxy-4-methylphenyl undecyl-ketoxime, nickel complexes of 1-phenyl-4- lauroyl-5-hydroxypyrazole, optionally with additional ligands.

2.6 Sterically hindered amines. such as, for example, bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis (1,2,6,6,6-pentamethylpiperidine) -4-yl) sebacate.

1010729 * 13 bi s (1-octyloxy-2,2,6,6-tetramethylpi peri di ne-4-yl) sebacate. n-butyl - 3,5-di-tert-butyl -4-hydroxybenzyl mal acid bis (1,2,2,6,6-pentamethylpiperidyDester, the condensation product of 1- (2-hydroxyethyl) - 2,2,6,6- tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N.N'-bis (2,2,6,6-tetramethyl-4-pperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1.3.5- triazine, tris (2.2.6.6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane tetraoate. 1.1 '- (1,2-ethanediyl ) -bi s (3,3,5,5-tetramethylpi perazi non).

4-benzoyl-2,2,6,6-tetramethylpi peridine. 4-stearyloxy-2.2.6.6-tetramethyl-pi-periodin, bis (1.2.2.6,6-pentamethyl-pi-periodyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert- butylbenzyl) malonate. 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-1riazaspiro [4.5] decane-2,4-dione. bis (1-octyloxy-2,2,6,6-tetramethylpi peridyl) sebacate, bi s (1-octyloxy-2,2.6,6-tetramethyl-15 piperidyl succinate, linear or cyclic condensation products of N.N'-bi s (2.2 .6,6-tetramethyl-4-pi-periodyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensation product of 2-chloro-4,6-di (4-n- butyl amino-2,2,6,6-tetramethyl-pi-periodyl) -1,3,5-tri-azine and 1,2-bis (3-aminopropylamino) ethane. the condensation product of 2-chloro-4, 6-di (4-n-butylamino-1,2,2,6,6-pentamethyl-pi-periodyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane. acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspi ro [4.5] decane-2,4-dione. 3-dodecyl-1- (2,2,6,6-tetramethyl 4-pi peri dyl) pyrroli di ne-2,5-dione, 3-dodecyl-1 - (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione. Mixture of 25 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethyl pi peri dine, the condensation product of N, N'-bi s (2,2,6,6-tetramethyl -4-pi peri dyl) hexa-methylenediamine and 4-cyclohexylamine o-2,6-dichloro-1,3,5-triazine. the condensation product of 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine, as well as 4-butyl amino-2,2,6,6-tetramethyl- Piperidine (CAS Reg. No. [136504-96-6]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecyl succinimide. N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro [ 4.5] decane, the reaction product of 7.7,9,9-tetra-methyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4.5] decane and epi-35 chlorohydrin, 1.1 -bis (1,2,2,6,6-pentamethyl-4-pi peridyloxycarbonyl) - 2- (4-methoxyphenyl) ethylene, N, N'-bisformyl-N.N'-bis (2,2,6,6-tetramethyl 4-piperidyl) hexamethylenediamine, diester of 4-methoxymethylene malonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly [methylpropyl - 101 07 2 9 14 3-oxy-4- (2, 2,6,6-tetramethyl-4-piperidyl)] siloxane. the reaction product I of maleic anhydride α-olefin copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7 Qxalic acid diamides. such as, for example, 4,4'-dioctyloxyoxanilide-2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide , 2-ethoxy-2'-ethyl-oxanilide, N.N'-bis (3-dimethylaminopropyl) oxalamide. 2-ethoxy-5-tert-butyl-2'-ethyl oxanilide and the mixture thereof with 2-ethoxy-2'-ethyl - = 5,4'-di-tert-butyloxanilide, mixtures of o- and p-methoxy- as well as of 10 o- and p-ethoxy-di-substituted oxanilides.

- 2.8 2- (2-hydroxylphenyl) -1.5-triazines. such as, for example, 2,4,6-tri s (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4- dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2- hydroxy-4-n-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-dimethyl phenyl) -1,3,5-triazine. 2- [2-Hydroxy-4- (2-hydroxy-3-butyloxypropyloxy) phenyl] -4,6 * bis (2,4-di-20 methyl) -1,3,5-triazine, 2- [2-hydroxy- 4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyl-. 4 oxy / tridecy 1 oxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-di-methyl methylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxy-, propoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1.3.5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2 -hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine. 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) - 6-phenyl-1.3.5-triazine. 2- {2-hydroxy-4- [3- (2-ethyl-hexyl-1-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl) -30 1,3,5-triazine.

3. Metal deactivators, such as, for example, N. N'-diphenyloxal acid diamide. N-salicylal-N'-salicyloylhydrazine, N.N'-bis (sali-cycloyl) hydrazine, N.N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazine. 3-salicyloylami no-1,2,4-triazole, bis (benzylidene) oxaa1- 35 acid dihydrazide, oxanilide, isophthalic dihydrazide, sebacic acid -, .. 1 .: bisphenyl hydrazide, NN'-di acetyl adi pinic acid dihydrazide, Ν, Ν'- bis- (sali cyloyl) oxalic acid dihydrazide, N, N'-bi s (sali cyloyl) thi opropionic dihydrazide.

1010729 15 4. Phosphites and phosphonites. such as, for example, triphenyl phosphite, di phenylalkyl phosphites, phenyl dialkyl phosphites, tri (nonylphenyl) phosphite, triauryl phosphite. trioctadecyl phosphite. di stearyl pentaerytri tol - di phosphi et. tri s (2,4-di-tert-butylphenyl) phosphite. di-sodecyl penta-erythritol diphosphite. bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bi s (2,6-di-tert-butyl-4-methyl phenyl) pentaerythritol diphosphite.

di isodecyloxypentaerythritol diphosphite. bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite. bis (2.4.6-tri (tert-butylphenyl) pentaerythri toldi phosphine, tri stearyl sorbi toltri phosphine et. tetrakis (2,4-di-tert-butylphenyl) -4,4'-bi phenylene di phosphonite, 6- Sooctyl oxy-2,4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1,2,2-dioxaphosphocin. 6-fluoro-2,4,8,10-tetra-tert-butyl - 12-methyl-dibenz [d, g] -1,3,2-dioxaphosphoci ne. Bi s (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bi s (2,4-di -tert-butyl-6-methylphenyl) ethylphosphite, 2.2 ', 2 "-nitrilo [triethyl-15 s (3,3', 5,5'-tetra-tert-butyl-1, -phenyl-2, 2'-diyl) phosphite]. 2-ethylhexyl (3.3'.5.5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite.

The following phosphites are particularly preferred: tris (2,4-di-tert-butylphenyl) phosphite (Irgafos® 168, Ciba-Geigy), tris (nonylphenyl) phosphite, 20 (CH3) 3C ^ xC (CH3) 3 Γ ( CH) c. ^ / C (CH3) 3

US 33 UN

(A) H3C-CH f-F T P-O-CH2CH2-N

25 \ (CH3) 3C ^ X ^ \ c (CH3) 3 C (CH3) 3 (CH3) 3c L J 3 (B) 30 P-O-CH2CH (C4H9) CHzCH3

(CH3) 3C

35 C (CH3) 3 Ï010729 16 (c ^ c-Q-0- {X} - ° - ^> c (ch3,3 (D)

C (CH3) 3 (CH3) 3C

5 C (CH3) 3 (ch3) 3c

C (CH3) 3 (CH3) 3C

(^) ^ 37 ^ 18 ® X f3 O C1eH37 o-7 '-o 15

Γ CH, ~ I

H3C c ch3 1 ^ 0 — p_och2ch3 (G) * sjcc .c ch3 j H3C CH3 3 —I 2: 5. Hydroxylamines. such as, for example, N, N-dibenzyl hydroxyl amine, N. N-diethyl hydroxyl amine. N, N-dioctyl hydroxyl amine, Ν, Ν-dilauryl-r hydroxyl amine. N. N-ditetradecylhydroxylamine. N. N-dihexadecylhydroxyl-amine, N, N-dioctadecylhydroxyl-amine, N-hexadecyl-N-octadecylhydroxyl-amine, N-heptadecyl-N-octadecyl-hydroxyl-amine, N. N-dialkyl-hydroxyl-amine from hydrogenated tallow fatty amine.

Ni-thrones, such as, for example, N-benzyl-al-phenyl nitron, N-ethyl-alpha-methyl nitron, N-octyl-alpha-heptyl nitron, N-lauryl-alpha-undecyl nitron, N-tetradecyl-alpha-tridecyl nitron, N-hexadecyl-a1 fa-pentadecyl nitron, N-octadecyl-alpha-heptadecyl nitron, N-hexadecyl-alpha-heptadecyl nitron, N-octadecyl-alpha-pentadecyl nitron, N-heptadecyl-alpha-heptadecyl nitron hexadecyl nitron, nitrons derived from N, N-dialkyl hydroxyl amine obtained from hydrogenated tallow fatty amine.

7, Thio-svnerqisten. such as, for example, thiodipropionic acid distillyl ester or thiodipropionic acid distearyl ester.

8. Peroxide scavengers. such as, for example, esters of 0-thio-dipropionic acid, for example the lauryl, stearyl, myristyl or tri-decyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zinc-dibutyl dithiocarbamate, dioctadecyl disulfide, pentaerythritol (/? - dodecyl mercapto) propionate.

9. Basic co-stabilizers, such as, for example, melamine, polyvinyl pyrrolidone, dicyandiamide. triallyl cyanurate. urea derivatives. hydrazine derivatives, amines. polyamides, polyurethanes, alkali metal and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg behenate. Mg stearate, Na-ricinoleate and K-pal mitate, antimony pyrocatecholate or zinc pyrocatecholate.

Nucleating agents, such as, for example, inorganic substances, such as e.g. talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of preferably alkaline earth metals; organic compounds such as mono- or polycarboxylic acids, as well as their salts, such as e.g. 4-tert-butyl benzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymers, such as ionic copolymers ("ionomers").

11. Fillers and reinforcing agents, such as, for example, calcium carbonate, silicates, glass fibers, glass balls, asbestos, talc. kaolin, mica, barium sulfate, metal oxides and hydroxides. soot. graphite, wood flour and flours or fibers of other natural products, synthetic fibers.

12. Other additives, such as plasticizers, lubricants, emulsifiers, pigments, rheology additives. catalysts, reducers, optical brighteners, flame retardants, anti-static agents and blowing agents.

13. Benzofuranones resp. indolinones, such as, for example, those 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) -phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxy-ethoxylphenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) -benzofuran-2-one. 3- (4-Acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di -tert- butyl benzofuran-2-one, 3- (3,4-dimethylphenyl) -5,7-di-tert-butylbenzo- 1010729 18 furan-2-one, 3- (2,3-dimethylphenyl) -5 7-di-tert-butylbenzofuran-2-one.

The stabilizers, with the exception of the benzofuranones listed under number 13, are added in concentrations of, for example, 0.01 to 10¾. based on the total weight of the polyamide, polyester or polyacetal to be stabilized *.

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

Particularly preferred additives are phenolic antioxidants (number 1 in the list), sterically hindered amines (number 2.6 in the list), phosphites and phosphonites (number 4 in the list) and peroxide scavengers (number 8 in the list).

15 Particularly interesting compositions are those. which, in addition to components (a) and (b), as a further additive, comprise at least one compound of the type of the organic phosphites or phosphonites (number 4 of the list).

Other preferred additional additives (stabilizers) are benzofuran-2-ones, such as those described inter alia 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 have been described.

Examples of such benzofuran-2-ones are compounds of the formula "i" jjcv.

n-V> R, R \ 2 H 11 wherein R'n is an unsubstituted or substituted carbocyclic or hetero-35 cyclic aromatic ring system; : R'i2 is hydrogen; R 14 is hydrogen, alkyl of 1 to 12 carbon atoms, cyclopentyl, cyclohexyl or chlorine; 1010729 19 R'13 has the meaning of R'12 or R'14 or is a remainder with the formula o

II

- (CH2) rC-OR'16,5 o o o

II II II

- (CH2) sCN (R'17) 2, (CH2) —c — o — A — O — C— (CH2) -— E, oooo II II II π 10 - (CH2) sC-NR \ —A- NR'1T-C- (CH2) SE, - (CH2 -C-NRVA-O-0- (0Η2) 5-Ε, o, __ oo II / \ ll Λ1Ι II o - (CH2) SC -— C - (CH2) -E, -CH2 -S-R19i -CH (C6H5) -C-OR'16 or -DE, where R '16 is hydrogen, alkyl of 1 to 18 carbon atoms, alkyl of 2 to 18 carbon atoms interrupted by oxygen or sulfur, dialkyl aminoalkyl containing a total of 3 to 16 carbon atoms, cyclopentyl, cyclohexyl, phenyl or phenyl substituted with 1 to 3 alkyl -20 radicals, which together do not contain more than 18 carbon atoms; s is 0. 1 or 2; the substituents R'17 are each independently hydrogen, alkyl of 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl substituted with 1 or 2 alkyl radicals, which together do not exceed 16 carbon contain substance atoms, are a radical of the formula -C2H40H, -C2H4-0-CtH2t + 10 or -C2H4-O--R'20, or together with the connecting nitrogen atom form a piperidine or morpholine residue, 30 t is 1 to 18; R'20 is hydrogen, alkyl of 1 to 22 carbon atoms or cycloalkyl of 5 to 12 carbon atoms; A is alkylene of 2 to 22 carbon atoms. which may be interrupted by nitrogen, oxygen or sulfur; 35 Ria hydrogen, alkyl of 1 to 18 carbon atoms, cyclopentyl. cyclohexyl, phenyl; phenyl or benzyl substituted with 1 or 2 alkyl radicals, which together do not contain more than 16 carbon atoms; R 19 is alkyl of 1 to 18 carbon atoms; D is -O-, -S-, -SO-, -SO2- or -C (R'21) 2-; The substituents R 21 are each independently hydrogen or C 1 -C 20 alkyl. the two radicals R'21 together contain 1 to 16 carbon atoms,

R'21 also phenyl or a radical of the formula 0 0 5 I II

- (CH2) s-Ó-0R'16 or - (CH2) s-C-N (R '17) 2. where s. R16 and R17 have the meanings mentioned above; - E is a residue with the formula 10? ', S

r · JL

I iL

I I R 'R'1Z h ”15 _ where R'u> R'12 and R'14 have the meanings mentioned above; and R'15 hydrogen, alkyl of 1 to 20 carbon atoms, cyclopentyl. cyclo-O-20 hexyl, chlorine or a radical of the formula -CH2 -loR * 16 Or o is -CH2---N (R'17) 2. wherein R'16 and R'17 have the above meanings, or R'1S together with R'14 is a tetramethylene residue.

? Those benzofuran-2-ones are preferred, wherein R13 is hydrogen, alkyl of 1 to 12 carbon atoms, cyclopentyl. cyclohexyl. chlorine or 0 0 7 a residue with the formula - (CH2) s-C-0R'16. - (CH2) s-t-N (R'17) 2 or -D-E.

30 where s. R16. R'17 D and E have the meanings given above, wherein R'16 is preferably hydrogen, alkyl of 1 to 18 carbon atoms, cyclopentyl or cyclohexyl.

Other preferred benzofuran-2-ones are those. wherein R 1 is phenyl or phenyl substituted with 1 or 2 alkyl radicals, which together do not contain more than 12 carbon atoms; R'1Z is hydrogen; R 14 is hydrogen or alkyl of 1 to 12 carbon atoms;

O

R 13 hydrogen, alkyl of 1 to 12 carbon atoms, - (CH 2) s -C-OR 16.

40 0 - (CH2) s— (ü-N (R'17) 2 or -D-E; R'15 is hydrogen, alkyl of 1 to 20 carbon 1010729 21

O O

dust atoms. -CH2J-OR'16 or -CH2 -d-N (R'17) 2, or R'15 together with R'14 is a tetramethylene residue. where s. R16, R17 D and E have the meanings given in the beginning 5.

Particularly interesting benzofuran-2-ones are also those, wherein R 3 is hydrogen, alkyl of 1 to 12 carbon atoms or -D-E; R'12 and R'14 are each independently hydrogen or alkyl of 1 to 4 carbon atoms; and R15 is alkyl of 1 to 20 carbon atoms, with D and E having the meanings mentioned above.

Finally, of special interest are also those benzofuran-2-ones, wherein R 1 is alkyl with 1 to 4 carbon atoms or -D-E; R'12 and R'14 are hydrogen; and R15 is alkyl of 1 to 4 carbon atoms, cyclopentyl or cyclohexyl. where a group is "C (R'21) 2" and E is a moiety with the formula 15?

R "JL

L iC> = o ’

20 '' l / V

R'i is "H" where the substituents R'21 are the same or different and each is alkyl of 1 to 4 carbon atoms and R'u. R'12. R '' and R'15 have the given meanings.

The amount of additional benzofuran-2-ones added can vary within wide limits and they can be in amounts of, for example, 0.0001 to 5 wt. preferably 0.001 to 2 wt%, more preferably 0.01 to 2 wt% are present in the compositions of this invention.

The incorporation of component (b) and optionally further additives into component (a) [polyamide, polyester or polyacetal] is done by known methods, for example before or after molding or also by applying the dissolved or dispersed component 35 ( b) on component (a), with or without subsequent evaporation of the solvent. Component (b) can also be in the form of a master composition. containing these components in a concentration of, for example, 2.5 to 25¾, are added to the materials to be stabilized [component (a)].

1010729 22

Component (b) can also be added before or during the polymerization or before cross-linking.

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

Component (b) can also be sprayed on the component (a) to be stabilized.

Component (b) can dilute other additives (e.g. the usual additives shown above) or their melts, so that they can also be sprayed on the component (a) to be stabilized together with these additives. Addition by spraying during the deactivation of the polymerization catalyst is particularly advantageous since it is possible to carry out the spraying using, for example, the steam used for the deactivation.

The polyamides, polyesters or polyacetals thus stabilized can be used in a very large number of forms, usually comprising films, fibers, filaments, molded articles, profiles, or as binders for paint systems, in particular powder coating compositions, adhesives or sealants.

Component (b) is particularly suitable for use as a processing stabilizer (heat stabilizer). For this, component (b) is usefully added to component (a) before or during processing.

Accordingly, a preferred embodiment of this invention is the use of component (b) as a stabilizer, in particular as a processing stabilizer (heat stabilizer), for stabilizing (a) polyamides, polyesters or polyacetals against oxidative, thermal and / or by light induced degradation with the proviso that if component (a) is a polyamide, then component (b) contains no metal hypophosphite and no copper salt of an organic acid; and with the proviso that as component (a) is a polyester-polyether copolymer, component (b) does not contain an organotin compound.

Component (b) is distinguished by its advantageous coloring behavior, ie little discoloration of the polyamides, polyesters and polyacetals during processing. Accordingly, this invention also relates to a method for stabilizing (a) a polyamide, polyester or polyacetal against oxidative , thermal and / or light-induced degradation, which method comprises incorporating, or applying to, the material of at least one component (b) with the proviso that if component (a) is a polyamide, then component (b ) contains no metal hypophosphite and no copper salt of an organic acid; and with the proviso that as component (a) is a polyester-polyether copolymer, component (b) does not contain an organotin compound.

The invention is illustrated in more detail in the following examples. Parts and percentages are by weight.

1010729 23

Example I: Stabilization of polyamide-12.

100 parts of unstabilized polyamide-12 granules (Grilamid®L 20 G, from EMS, Switzerland) are pulverized by cryogenic grinding and loaded with the stabilizers listed in Table A. This mixture is mixed in a Henschel mixer for 2 minutes at 70 ° C. The powder thus obtained is then dried at 80 ° C for 6 hours and then extruded at a maximum of 210 ° C in a twin screw extruder (Berstorff type) and then granulated. The obtained granules are injected at a maximum of 220 ° C in an injection molding machine. ; (Engel type) injection molded into tensile rods with a thickness of 1.0 mm and a length of 67 mm. The yellowness index (YI) of these tie rods is determined according to ASTM D 1925-70. Low YI values indicate little discoloration, high YI values indicate strong discoloration of the samples. The less discoloration, the more effective the stabilizer or the stabilizer mixture. The results are summarized in Table A.

1010729 24

Table A:

Example Stabilizers Yellowness index (dumbbells)

Iaa) - 6.7

Iba) 0.25¾ Irganox®245c) 8.9 = 5 Ica) 0.50¾ Irganox®245c) 9.6

Ida) 0.25¾ Irganox®1098d) 9.2

Iea) 0.50¾ Irganox®1098d) 10.7

If0 0.25 component (b) e) 6.3

Igb) 0.50¾ component (b) e) 6.4 10 Iha) 0.25¾ Irganox®245c) 6.8 0.25¾ Irgafos®168f)

Iia) 0.25¾ Irganox®1098d) 7.6 0.25¾ Irgafos®168f)

Ijb) 0.25¾ component (b) e> 5.7 0.25¾ Irgafos®168f)

Ika) 0.25¾ Irganox®245c) 5.3 0.25¾ Irgafos®129)

Ila) 0.25¾ Irganox®1098d) 6.0 0.25¾ Irgafos®129) 15 Imb) 0.25¾ component (b) e> 3.4 0.25¾ Irgafos®129) a) Comparative example.

b) Example of this invention.

1010723 25 c) Irganox®245 (Ciba Spezialitatenchemie AG) is a compound of the formula AO-1 h3c h c CH3 5 Η3 ° "_) = \ h ° __ / ^^ CH3

HO— (v / Λ> —CH2 — CH2 — c — o - (CH2CH20) 3 — c — CHa-CHa — U n OH

ch3 ch3 10 (A01) d) Irganox®1098 (Ciba Spezialitatenchemie AG) is a compound with the formula A02 H-C u c CH3 15 H0 = \ _ Η ° _ / K ^ CHa

HO \\ // ° Η2— CH — c — NH— (CH2) 6 — nh-c — ch2-ch2 — U Λ — OH

ΟΗ3Χ ° Η3 H3C CH3 20 (A02)

e) Component (b) is the compound of the formula I.

H3C LI q CH.

3 \ ^ CH3 H3 ^ n / 3 25 H0 = \ Η Π _ / = CCH3

HO - /) - CH2 — CH — C — NH— (CH2) 6 — NH - C — CHr CH ,, - Λ Λ — OH

ch3 ch3 30 (,) f) Irgafos®168 (Ciba Spezialitatenchemie AG) is tris (2,4-di-tert-butylphenyl) phosphite.

g) Irgafos®12 (Ciba Spezialitatenchemie AG) is 2,2 ', 2 "-nitrilo [triethyl-tris (3,3', 5.5 '-tetra-tert-butyl-1,1' -diphenyl-2,2 ' -diyl) phosphite], 35 Chemical Abstract Registration Number: 80410-33-9, and represents the compound of formula B.

1010729 26 (CH3) 3C- ^ r ^ C (CH3) 3 I jT V — O — CH2CH —- N (B)

(CH

C (CH3) 3 L - * 3 10

Example II: Stabilization of polyamide-6.

100 parts of unstabilized polyamide-6 granules (Ultramid®B3S. 15 from BASF) are pulverized by cryogenic grinding and loaded with the stabilizers listed in Table B. This mixture is then mixed in a Henschel mixer for 2 minutes at 70 ° C. The powder thus obtained is then dried at 80 ° C for 6 hours and extruded at a maximum of 240 ° C in a twin screw extruder (Berstorff type) and then granulated. The granules obtained are injection molded into small rods of 4 x 6 mm thickness and 50 mm length in an injection molding machine at a maximum of 240 ° C. The rods are aged at 150 ° C in an air-circulating oven. The time during which the impact strength of the rods decreases to 80 kJ / m2 is measured in hours. 25 The longer the time, the better the stabilization. The results are summarized in Table B.

"

Table B: Impact strength in an aging test in an oven at 150 ° C

Example Stabilizer Time in hours at 150 ° C until an impact strength of 80 kJ / m2 is achieved 30 IIaa) - 2 IIba) 0.25¾ Irganox®245c) 28 IIca) 0.25¾ Irganox®1098d) 30 IIdb) 0.25¾ component (b) e> 38 2ie the end of Table A for the explanation of footnotes a) to 1010729 t 27 and e).

Example III: Stabilization of a Polyoxymethylene Copolymer (POM) 100 parts of unstabilized POM copolymer (Hostaform®C. Hoechst) is mixed with 0.3¾ calcium stearate and with the stabilizers listed in Tables C. D and E. The powder is then extruded at a maximum of 190 ° C. Some of these granules are injection molded into plates with a thickness of 2 mm at a maximum of 200 ° C. a width of 40 mm and a length of 60 mm injection-mold. The other part of the granules is injection-molded at a maximum of 200 ° C into small rods with a thickness of 4 x 6 mm and a length of 50 mm.

Under a stream of air, a thermogravimetric measurement is carried out on a portion of these plates at 220 ° C isothermally. The time until the pictures 3¾. Losing 6¾ and 10¾ of their weight is measured in minutes. The longer the time. the better the stabilization. The results are summarized in Table C.

Table C: Thermogravimetric measurement at 220 ° C

Example Stabilizer Time in minutes to reach a weight loss of 3¾ 6¾ 10¾

Ilia3 '0.30¾ Irganox®245c) 53 70 88 11 Iba) 0.30¾ Irganox®1098d) 78 103 127 IIIcb> 0.30¾ component (b) e) 82 114 157 25 See the end of Table A for the explanation of the footnotes a) to e).

An aging test is performed in an oven at 140 ° C on another portion of the plates. The slides are aged at 140 ° C in an air circulating oven and the time until the slides lose 2¾ of their weight is measured in hours. The longer the time. the better the stabilization. The results are summarized in Table D.

1010729 28

Table D: Weight loss in an aging test in an oven at 140 ° C

Example Stabilizer Time in hours until weight loss of 2¾ is achieved IIIda) 0.30¾ Irganox®245c) 1300 5 IIIea) 0.30¾ Irganox®1098d) 2150 IIIfb) 0.30¾ component (b) e) 2700

See the end of Table A for the explanation of footnotes a) to e).

The 4 x 6 mm thick and 50 mm long bars are also heated at 140 ° C

subjected to an aging test in an air circulating oven, *: ι: ί measuring the time in hours until the impact strength of the -j bars has decreased from originally 110 kj / m2 to 90 kJ / m2. How: i longer time. the better the stabilization. The results are summarized in Table E.

Γ "τη

Table E: Impact strength in an aging test in an oven at 140 ° C

Example Stabilizer Time in hours at 140 ° C until an impact strength of 90 kJ / m2 is achieved 11 Iga) 0.30¾ Irganox®245c) 770 20 11 Iha> 0.30¾ Irganox®1098d) 800 IIIib) 0.30¾ component (b ) e> 1250 ---- See the end of Table A for the explanation of footnotes aj to e).

1010729

Claims (11)

A composition comprising a) a polyamide, polyester or polyacetal which is subject to oxidative, thermal or light-induced degradation and b) the compound of the formula IH, CH, C, CH3 3 \ CH3 3 \ / ίί ίί CCH3 10 HO— (λ // - ch-ch2— c - nh— (ch2) 6-nh-c-ch2-ch2— ^ Λ— OH ch3 ch3 O). With the proviso that if component (a) is a polyamide, then the composition will not contain any metal hypophosphite and no copper salt of an organic acid and provided that as component (a) is a polyester-polyether copolymer, then the composition will not contain an organotin compound contains. A composition according to claim 1, wherein the polyamide is polyamide-6, polyamide-6,6, polyamide-4,6, polyamide-11 or polyamide-12 or a copolymer thereof. The composition of claim 11, wherein the polyester is PET, PETG or PBT or a copolymer thereof. The composition of claim 1, wherein the polyacetal is a homopolymer or a copolymer. The composition of claim 1, wherein component (b) is present in an amount of 0.01 to 1% based on the weight of component (a). The composition of claim 1, further comprising further additives in addition to components (a) and (b). The composition of claim 6, wherein the further additives are phenolic antioxidants, light stabilizers and / or processing stabilizers. The composition of claim 6, wherein the further additive is at least one compound of the organic phosphites or phosphonites type. 1010729 w. The composition of claim 6, wherein the further additive is at least one benzofuran-2-one type compound. Method for the stabilization of (a) a polyamide, polyester or polyacetal against oxidative, thermal and / or light-induced degradation, which incorporates, or applies to, these materials of at least one component (b) according to claim 1, provided that if component (a) is a polyamide, then component (b) contains no metal hypophosphite and no copper salt of an organic acid; and with the proviso that as component (a) is a polyester-polyether copolymer, component (b) does not contain an organotin compound. Use of component (b) according to claim 1 as a stabilizer for protecting (a) polyamides, polyesters or polyacetals against oxidative, thermal and / or light-induced degradation, with the proviso that as component (a) is a polyamide then component (b) does not contain a metal hypophosphite and no copper salt of an organic acid; and with the proviso that as component (a) 15 is a polyester-polyether copolymer, component (b) does not contain an organotin compound. - = - M 1010729