FR2772036A1 - STABILIZATION OF POLYAMIDE, POLYESTER AND POLYACETAL - Google Patents

Abstract

This invention relates to compositions which comprise a) a polyamide, polyester or polyacetal, and b) as a stabilizer the compound of formula I (CF DRAWING IN BOPI) with the proviso that, if component (a) is a polyamide, then the composition does not contain a metal hypophosphite or a copper salt of an organic acid of the use of the compound of formula I for the stabilization of a polyamide, a polyester or a polyacetal against oxidative degradation , thermal and/or light-induced, as well as a method for stabilizing these plastic materials.

Description

The present invention relates to compositions comprising a polyamide,

  a polyester or polyacetal also relates to a specific phenolic antioxidant, their use for the stabilization of polyamides, polyesters or polyacetals against oxidative, thermal and / or light-induced degradation, and a method for

  the stabilization of these plastics.

  It is known from the patent description

  No. 3,691,131 and 3,860,558 that the polyamides can be stabilized with phenolic antioxidants in the presence of metal hypophosphites, such as potassium hypophosphite and sodium hypophosphite, and copper salts.

organic acids.

  In polyamides, polyesters or polyacetals, these mixtures of known stabilizers can not satisfy all the demands they are subject to. It is known that such stabilizer mixtures reduce the initial color as well as the color development of the polyamide during oven aging and further reduce the degradation of the mechanical properties of the polyamide during oven aging. and

exposure to light.

  It has now been found that a specific phenolic antioxidant, which is selected according to

  descriptions of U.S. Patent Nos. 3,691,131 and

  No. 3,860,558, is particularly suitable as a stabilizer for polyamides, polyesters or polyacetals in the absence of metal hypophosphites.

  and copper salts of organic acids.

  Accordingly, the present invention contemplates compositions comprising: a) a polyamide, a polyester or a polyacetal, which is subjected to oxidative, thermal or light-induced degradation, and b) the compound of formula I

H3C CHH3 CH3

H3C O X CH3

  ## STR5 ## wherein CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2

CH3 CH3

  provided that if component (a) is a polyamide, then the composition contains no metal hypophosphite and no copper salt of a

organic acid.

  Component (b) of the novel composition, or the compound of formula I, is known and has the Chemical Abstracts Registry Number [37042-77-6]. The preparation of the compound of formula I is disclosed in GB-A-1,251,840, Example 1,

page 5.

  By polyamides is meant aromatic and aliphatic polyamides or copolyamides which are derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or their corresponding lactams. Suitable polyamides are, for example, PA 6, PA 11, PA 12, PA 46, PA 6.6, PA 4.6, PA 6.9, PA 6.10 or PA 6.12. PA 10.12. PA 12.12 and

  also amorphous polyamides of the Trogamid PA 6-3-

  T and Grilamid TR 55. The polyamides of the type cited are

  commonly known and commercially available.

  Useful 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 polyamide 6 modified elastomer,

  or polyamide 6.6 mixed with polypropylene.

  The polyesters used can be homo-

  or copolyesters which are composed of hydroxycarboxylic acids or of dicarboxylic acids and aliphatic, cycloaliphatic or aromatic diols. The aliphatic dicarboxylic acids may contain from 2 to 40 carbon atoms, the cycloaliphatic dicarboxylic acids of 6 to 10 carbon atoms, the aromatic dicarboxylic acids of 8 to 14 carbon atoms, the aliphatic hydroxycarboxylic acids of 2 to 12 carbon atoms, and aromatic hydroxycarboxylic acids, for example

  cycloaliphatic, of 7 to 14 carbon atoms.

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

16 carbon atoms.

  Aromatic diols are those where two hydroxyl groups are attached to one or more radicals

aromatic hydrocarbons.

  The polyesters may also be branched with small amounts, for example from 0.1 to 3 mol%, based on the dicarboxylic acids present, of monomers having a higher functionality than the difunctional monomers (eg

  pentaerythritol, trimellitic acid, 1,3,5-

  tri (hydroxyphenyl) benzene, 2,4-dihydroxy-

  benzoic acid or 2- (4-hydroxy-phenyl) -2- (2,4-dihydroxy-

  phenyl) propane). Polyesters consisting of at least 2 monomers may have a random distribution or they

  may 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 malonic acid, succinic acid, pimelic acid, adipic acid, trimethyladipic acid, sebacic acid, azelaic acid and dimeric acids (dimerization products of unsaturated aliphatic carboxylic acids, such as oleic acid), alkylated malonic and succinic acids such as octadecylsuccinic acid. Cycloaliphatic dicarboxylic acids

  are: 1,3-cyclobutane

  dicarboxylic acid, 1,3-cyclopentanedicarboxy-

  1,3- and 1,4-cyclohexanedicarboxylic acid, 1,3- and 1,4- (dicarboxylmethyl) cyclohexane,

  4,4'-dicyclohexyldicarborylic acid.

  Suitable aromatic dicarboxylic acids are: in particular the acid

  terephthalic acid, isophthalic acid,

  phthalic acid, and also 1,3-, 1,4-, 2,6- or 2,7-naphthalenedicarboxylic acid,

  4,4'-diphenyldicarboxylic acid, 4,4'-acid

  diphenylsulfonedicarboxylic acid, 4,4'-benzo

  phénonedicarboxylique. 1,1,3-trimethyl-5-carboxyl

  3- (p-carboxylphenyl) indane, 4,4'-diphenyl-

  ether-dicarboxylic acid, bis-p- (carboxylphenyl)

  methane or bis-p- (carboxylphenyl) ethane.

  The aromatic dicarboxylic acids are preferred, and among these in particular the acid

  terephthalic acid, isophthalic acid, and 2,6-

naphthalenedicarboxylic.

  Other suitable dicarboxylic acids are those containing -CO-NH- groups; they are described in DE-A-2,414,449. Dicarboxylic acids containing nitrogen heterocycles are also suitable, for example those are derived from carboxyl-alkylated, carboxyl-phenylated or carboxybenzylated monoamino-s-triazinodicarboxylic acids (see DE-A-2,121,184 and 2,533,675), mono or bishydantoins, benzimidazoles or optionally halogenated parabanic acid. In this context, the carboxyalkyl groups may contain

3 to 20 carbon atoms.

  Suitable aliphatic diols are linear and branched aliphatic glycols, especially those containing from 2 to 12, preferably from 2 to 6, carbon atoms in the molecule, for example: ethylene glycol, 1,2- and 1-carbon. , 3-propylene glycol, 1,2-, 1,3-, 2,3- or

  1,4-butanediol, pentylglycol, neopentyl-

  glycol, 1,6-hexanediol, 1,12-dodecanediol. A suitable cycloaliphatic diol is, for example, 1,4-dihydroxycyclohexane. Other aliphatic diols

  Examples are 1,4-bis (hydroxymethyl) -

  cyclohexane, aliphatic-aromatic diols, such as

  that p-xylylene glycol, or 2,5-dichloro-p-

  xylylene glycol, 2,2- (O-hydroxyethoxyphenyl) -

  propane and polyoxyalkylene glycols, such as ethylene glycol, triethylene glycol, polyethylene glycol or polypropylene glycol. The alkylenediols are preferably linear and

  preferably contain from 2 to 4 carbon atoms.

  Preferred diols are alkylene diols,

  1,4-dihydroxycyclohexane and 1,4-bis (hydromethyl) -

  cyclohexane. Ethylene is particularly preferred

  glycol, 1,4-butanediol and 1,2- and 1,3-

propylene glycol.

  Other suitable aliphatic diols are -6-

  5-hydroxyalkyl bisphenols, in particular 3-hydroxy-

  ethylated. such as 2,2-bis [4 '- (3-hydroxyethoxy) -

  phenyl] propane. Other bisphenols are mentioned below.

  after. Another group of suitable aliphatic diols is that of the heterocyclic diols described in DE-A-1,812,003. DE-A-2,342,432, DE-A-2,342,372 and DE-A-2,453,326. are: N, N'-bis (β-hydroxyethyl) -5,5-dimethylhydantoin, N, N'bis (β-hydroxypropyl) -5,5-dimethylhydantoin,

  methylene-bis- [N- (-hydroxyethyl) -5-methyl-5-ethyl]

  hydantoin], methylene-bis- [N- (3-hydroxyethyl) -5.

  dimethylhydantoin], N, N'-bis- (β-hydroxyethyl) -

  benzimidazolone, N, N'-bis (5-hydroxyethyl) - (tetra-

  chloro) -benzimidazolone or N.N'-bis- (O3-hydroxy-

  ethyl) - (tetrabromo) benzimidazolone. Suitable aromatic diols are mononuclear diphenols and, in particular. dinuclear diphenols which carry a hydroxyl group on each aromatic ring. By the aromatic term, preference should be given to aromatic hydrocarbon radicals. for example phenylene or naphthylene. In addition, for example to hydroquinone. the

  resorcinol or 1.5-, 2.6- and 2.7-

  dihydroxynaphthalene, it is particularly appropriate to mention bisphenols which can be represented by the following formulas:

R 'R' R 'R'

HO OH HO

A A

HO

R3 R "R" R "

- 7 -

R 'R'

HO, _N COH

> s A - <-

R "R"

R 'R'

HO OH

A A

R "R"

R 'R'

HO OH

A --f - A ---- jA

R "R"

R 'R'

HO O

R R "

  The hydroxyl groups may be in the meta position and, in particular, in the para position. R 'and R "in these formulas may be an alkyl group containing from 1 to 6 carbon atoms, a halogen atom, such as a chlorine atom or a bromine atom, and, preferably, hydrogen, A may be a direct bond, or oxygen atoms

  or sulfur. -SO-, -SO2-,> C = O, -P (O) (C1-C6) alkyl

  C20). unsubstituted or substituted alkylidene,

cycloalkylidene or alkylene.

  Examples of unsubstituted or substituted alkylidene are: ethylidene, 1, 1- or 2,2-propylidene, 2,2-butylidene, 1,1-isobutylidene, pentylidene, hexylidene. heptylidene, octylidene, dichloroethylidene. trichloroethylidene. Examples of unsubstituted or substituted alkylene are methylene, ethylene, phenylmethylene, diphenylmethylene. methylphenylmethylene. of the

  Examples of cycloalkylidene are cyclopentylidene.

  cyclohexylidene. cycloheptylidene and cyclooctylidene.

  Examples of bisphenols are: bis ether (p-

  hydroxyphenyl) or thioether bis (p-hydroxy-

  phenyl). bis (p-hydroxyphenyl) sulfone. the bis

  (p-hydroxyphenyl) methane, bis (4-hydroxyphenyl) -

  2,2'-biphenyl, phenylhydroquinone. the 1,2-bis (p-

  hydroxy-phenyl) ethane, 1-phenyl-bis- (p-hydroxy)

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

  methane, diphenyl-bis (p-hydroxy-phenyl) ethane. the

  bis- (3,4-dimethyl-4-hydroxyphenyl) -sulfone, the bis-

  (3 .5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene.

  bis (3,5-dimethyl-4-hydroxy-phenyl) -m-diisopropyl-

  benzene, 2,2-bis- (3'5'-dimethyl-4'-hydroxyphenyl) -

  propane, 1,1- or 2,2-bis (p-hydroxyphenyl) -

  butane, 2,2-bis- (p-hydroxy-phenyl) hexafluoro-

  propane, 1,1-dichloro- or 1,1,1-trichloro-2,2-

  bis (p-hydroxyphenyl) ethane, 1,1-bis (p-hydroxy)

  phenyl) 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 polyesters of 4- acid

  hydroxycyclohexanecarboxylic acid or 4-

  hydroxybenzoic. Polymers which may contain mainly ester bonds but also other bonds, for example polyesteramides or

  polysster-imides, are also suitable.

  Polyesters containing aromatic dicarboxylic acids are most important. in particular the polyalkylene terephthalates. Therefore. the molding compounds according to the invention are preferred, in which the polyester is composed of at least 30 mol%, preferably at least 40 mol%, aromatic dicarboxylic acids and at least in moles, preferably at least 40 mol%, of alkylenediols preferably containing from 2 to 12

  carbon atoms, relative to the polyester.

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

  terephthalic and / or isophthalic acid.

  Polyesters which are particularly suitable are PET, PETG (glycol-modified polyethylene terephthalate) or PBT (polybutylene terephthalate) and corresponding copolymers.

  Particularly preferred is PET and its copolymers.

  Polyacetals are, for example,

  homopolymers or copolymers of paraformaldehyde.

  such as in particular polyoxymethylene (POM), and polyoxymethylenes which contain comonomers, such as ethylene oxide and polyacetals which are modified by thermoplastic polyurethanes,

acrylates or by MBS.

  Usable compositions are those described above wherein component (b) is present in an amount of 0.01 to 1%, preferably 0.02 to 0.8%, e.g. 0.03 to 0 , 6%, by

relative to the weight of component (a).

- 10 -

  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 mononenols, for example 2,6-di-

  tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethyl-

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

  butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-iso-butyl-

  phenol, 2,6-dicyclopentyl-4-methylphenol, 2-Ca.-methyl-

  cyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-

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

  butyl-4-methoxymethylphenol, linear nonylphenols or

  branched in the side chains, for example 2,6-

  di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methyl)

  undec-1-yl) -phenol, 2,4-dimethyl-6- (1-methylhepta)

  dec-the-yl) -phenol. 2,4-dimethyl-6- (methyl-the-tridec-

1-yl) -phenol and mixtures thereof.

  1.2. Alkylthiomethylphenols, for example 2,4-

  dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthio-

  methyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethyl-

  phenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.

  1.3. Hydroquinones and alkylated hydroquinones,

  for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-

  tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone,

  2,6-di-phenyl-4-octadecyloxyphenol, 2,6-di-tert-butyl-

  hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisol, 3,5-

  di-tert-butyl-4-hydroxyanisol, 3,5-di-stearate

  tert-butyl-4-hydroxyphenol, bis (3,5-di-

tert-butyl-4-hydroxyphenyl).

  1.4. Tocopherol, for example α-tocopherol, β-tocopherol, γ-tocopherol, 5-tocopherol and their

mixtures (vitamin E).

  1.5. Hydroxyethyl thiodiphenyl ethers, for example 2,2'thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'thiobis (6-tert-butyl)

- 11 -

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

  phenol), 4,4'-thiobis (3,6-di-sec-amylphenol), disulfide

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

  1.6. Alkylidenebisphenols, for example 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4ethylphenol), 2,2'-methyl

  ene-bis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-

  Methylenebis (4-methyl-6-cyclohexylphenol) 2,2'-

  Methylenebis (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'-methylenebis [6- (a-methyl-

  benzyl) -4-nonylphenol], 2,2'-methylenebis [6- (c, a-di)

  methylbenzyl) -4-nonylphenol], 4,4'-methylene-bis- (2,6-

  di-tert-butylphenol), 4,4'-methylene-bis (6-tert-butyl)

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

  methyl-phenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-

  hydroxy-benzyl) -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, bis [3,3-bis (3'-tert-butyl-4'-hydroxy)

  ethylene glycol phenylbutyrate, bis- (3-tert-butyl-4-

  hydroxy-5-methylphenyl) -dicyclopentadiène,

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

  methylbenzyl) -6-tert-butyl-4-methylphenyl], 1,1-bis-

  (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis-

  di-tert-butyl-4-hydroxyphenyl) -propane, 2,2-bis- (5-

  tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecyl

  mercaptobutane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy)

2-methylphenyl) pentane.

  1.7. O-compounds. N- and S-benzyl, by

  Example 3,5,3 'ether, 5'-tetra-tert-butyl-4,4'-di-

  hydroxy-dibenzyl, 4-hydroxy-3,5-dimethylbenzyl-

  octadecyl mercaptoacetate, 4-hydroxy-3,5-di-tert-

  tridecyl butylbenzyl mercaptoacetate, tris (3,5-

  di-tert-butyl-4-hydroxybenzyl) amine, dithiotere-

- 12 -

  bis (4-tert-butyl-3-hydroxy-2,6-dimethyl) phthalate

  benzyl), bis- (3,5-di-tert-butyl-4-hydroxy-

  benzyl), 3,5-di-tert-butyl-4-hydroxybenzyl mercapto

isooctyl acetate.

  1.8. Hydroxybenzylated malonates, for example 2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonates of

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

  benzyl) -malonate of dioctadecyl, 2,2-bis- (3,5-di-

  tert-butyl-4-hydroxybenzyl) didodecyl malonate

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

  bis (4- (1,1,3,3-tetramethylbutyl) benzyl) malonate

  phenyl]. 1.9. Hydroxybenzyl aromatic compounds,

  for example 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxy-

  benzyl) -2,4,6-trimethylbenzene, 1,4-bis- (3,5-di-tert-

  butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris- (3,5-ditert-butyl-4-hydroxy-benzyl) phenol. 1.10. Triazine compounds, for example

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

  hydroxy-anilino) -1,3,5-triazine, 2-octylmercapto-4,6-

  bis- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-Trianon

  zine, 2-octylmercapto-4,6-bis- (3,5-di-tert-butyl-4-

  hydroxy-phenoxy) -1,3,5-triazine, 2,4,6-tris- (3,5-di-

  tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, isocyanurate

  spleen of 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxy-

  benzyl), 1,3,5-tris- (4-tert-butyl) -3-isocyanurate

  2,6-hydroxy-dimethyl-benzyl), 2,4,6-tris- (3,5-di-

  tert-butyl-4-hydroxyphenyl-ethyl) -1,3,5-triazine,

  1,3,5-tris- (3,5-di-tert-butyl-4-hydroxy-phenyl

  propionyl) -hexahydro-1,3,5-triazine, 1,3,5-tris- (3,5-dicyclohexyl-4-hydroxy-benzyl) isocyanurate. 1.11. Benzyl phosphonates, for example

  2,5-di-tert-butyl-4-hydroxybenzylphosphonate di

  methyl, 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate

* diethyl, 3,5-di-tert-butyl-4-hydroxybenzyl-

  dioctadecyl phosphonate, 5-tert-butyl-4-hydroxy-3-

- 13 -

  dioctadecyl methylbenzyl phosphonate, Ca

  3,5-di-tert-butyl-4- ethyl acid monoethyl ester

hydroxybenzyl phosphonic.

  1.12. Acylaminophenols, for example 4-hydroxy-

  anilide of lauric acid, 4-hydroxyanilide

  stearic acid. N- (3,5-di-tert-butyl-4-hydroxy-

phenyl) octyl carbamate.

  1.13. Esters of β- (3,5-di-tert-butyl)

  4-hydroxyphenylpropionic with monohydric alcohols or

  polyhydroxyl, for example methanol, ethanol, n

  octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-

  nonanediol, ethylene glycol, 1,2-propanediol,

  neopentyl glycol, thiodiethylene glycol, diethylene

  glycol, triethylene glycol. pentaerythritol, iso-

  tris (hydroxyethyl) cyanurate, acid amide

  N, N'-bis (hydroxyethyl) oxalic acid, 3-thiaundecanol, 3-

  thiapentadecanol, trimethylhexanediol, trimethylol

  propane, 4-hydroxy-methyl-1-phospha-2,6,7-trioxabi-

cyclo [2.2.2] octane.

  1.14. Esters of B- (5-tert-butyl-4-)

  hydroox-3-methylphenylpropionic acid with monohydric or polyhydric alcohols, for example methanol,

  ethanol, n-octanol, i-octanol, octadecanol, 1,6-

  hexane-diol, 1,9-nonanediol, ethylene glycol, 1,2-

  propanediol, neopentyl glycol. thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, acid amide

  N, N'-bis (hydroxyethyl) oxalic acid, 3-thiaundecanol, 3-

  thiapenta-decanol, trimethylhexanediol, trimethylol

  propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabi-

cyclo [2,2,2] octane.

  1.15. Esters of B-f3.5-dicyclohexyl-4- acid

  hydroxyphenylpropionic with monohydric alcohols or

  polyhydroxy, for example methanol, ethanol. not-

  octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-

  nonanediol, ethylene glycol, 1,2-propanediol,

- 14 -

  neopentyl glycol, thiodiethylene glycol, diethylene

  glycol. triethylene glycol, pentaerythritol, isocyanate

  spleen tris (hydroxyethyl), amide of N, N'-

  bis (hydroxyethyl) oxalic acid. 3-thiaundecanol, 3-thia-

  pentadecanol, trimethylhexanediol, trimethylol

  propane, 4-hydroxy-methyl-1-phospha-2,6,7-trioxabi-

cyclo [22.2.2] octane.

  1.16. Esters of 3,5-di-tert-butyl-4- acid

  hydroxyphenylacetic acid with mono- or polyhydric alcohols

  hydroxyl, for example methanol, ethanol,

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

  glycol, 1,2-propanediol, neopentyl glycol, thio-

  diethylene glycol, diethylene glycol, triethylene

  glycol, pentaerythritol, isocyanurate of tris

  (hydroxyethyl), diamide of N, N'-bis-

  (hydroxyethyl) -oxalic, 3-thiaundecanol, 3-thiapenta

  decanol, trimethylhexanediol, trimethylolpropane, 4-

  hydroxymethyl-phospha-2,6,7-trioxabicyclo [2.2.2] -

octane.

  1.17. Amides of 9-f3,5-di-tert-butyl-acid

  4-hydroxyphenylpropionic, for example N, N'-bis-

  di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene

  diamine. N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenyl

  propionyl) trimethylenediamine, NN'-bis- (3,5-di-tert-

  butyl-4-hydroxyphenylpropionyl) hydrazide, N, N'-bis [2-

  (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) -

  ethyl] -oxamide (NaugardOXL-1 supplier Uniroyal).

1.18. Ascorbic acid (vitamin C)

  Amino antioxidants for example NN'-

  di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-

  p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-

  phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-

  phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylene

  -diamine, N, N'-dicyclohexyl-p-phenylene-amine, N, N'-

  diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-

  phenylenediamine, N-isopropyl-N'-phenyl-p-phenylene

- 15 -

  diamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylene

  diamine, N- (1-methylheptyl) -N'-phenyl-p-phenylene

  diamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine,

  4- (p-toluènesulfamoyl) diphenylamine. N, N'-dimethyl

  N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine,

  N-allyl-diphenylamine, 4-isopropoxydiphenylamine, N-

  phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-

  naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-di-tert-octyldiphenylamine,

  4-n-butylamino phenol, 4-butyrylaminophenol, 4-nonanea

  noylamino-phenol. 4-dodecanoylaminophenol, 4-octadec

  noylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di-

  tert-butyl-4-dimethylamino-methylphenol. 2,4'-Diamino

  diphenylmethane. 4,4'-diamino-diphenylmethane, N, N, N ', N'tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis [(2 (methylphenyl) amino] ethane, 1,2-bis (phenyl)

  amino) propane, (o-tolyl) -biguanide, bis [4- (1'.3'-

  dimethylbutyl) phenyl] amine. N-phenyl-1-naphthyl-amine

  tert-octyl, mixture of tert-butyl / tert-octyldiphenyl-

  mono- and dialkyl amines, e. mixture of mono- and dialkylated nonyldiphenylamines, mixture of mono- and dialkylated dodecyldiphenylamines, mixture of mono- and dialkylated isopropyl / isohexyldiphenylamines, mixture of tert-butyldiphenylamines mono- and

  dialkylated 2,3-dihydro-3,3-dimethyl-4H-1,4-benzoate

  thiazine, phenothiazine, mixture of tert-butyl / tert-

  mono- and dialkylated octylphenothiazines, a mixture of

  mono- and dialkylated tert-octyl-phenothiazines. N-allyl

  phenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-

  ene, N, N-bis (2,2,6,6-tetramethylpiperid-4-yl) -hexa

  methylenediamine, bis (2,2,6,6-tetraacetate) sebacate

  methylpiperid-4-yl), 2,2,6,6-tetramethylpiperidin-4-

  one, 2,2,6,6-tetramethylpiperidin-4-ol.

  2. UV absorbers and photoprotective agents 2.1. 2- (2'-Hydroxyphenylbenzotriazoles, for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole,

- 16 -

  2- (3 ', 5'-di-tert-buty1-2'-hydroxyphenyl) benzotriazole,

  2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2-

  (2'-hydroxt-5 '- (1,1,3,3-tetramethylbutyl) -phenyl) -

  benzo-triazole, 2- (3 ', 5'-di-tert-butyl-2-hydroxy-

  phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl) -2'-

  hydroxy-5'-methylphenyl) -5-chlorobenzotriZole, 2-

  (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzoate

  triazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotri-

  azole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxy-phenyl) benzoate

  triazole, 2- (3 ', 5'-bis- (α-dimethylbenzyl) -2'-

  hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl)

  2'-hydroxy-5 '- (2-octyloxycarbonyléthyl) -phenyl-5-chloro

  benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyl)

  oxy) -carbonyléthyl] -2'-hydroxyphenyl) -5-chloro-benzo

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

  carbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl)

  2'-hydroxy-5 '- (2-octyloxycarbonyléthyl) phenyl) -benzo

  triazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) -

  carbonylethyl] -2'-hydroxyphenyl) benzo-triazole, 2- (3'-

  dodecyl-2-hydroxy-5'-methylphenyl) benzotriazole, 2-

  (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxy-carbonyl-

  ethyl) -phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl)

  phenol]: transferification product of 2- [3'-tert-

  butyl-5 '- (2-methoxycarbonyl-ethyl) -2'-hydroxyphenyl] -

  2H-benzotriazole with polyethylene glycol 300: [R-

  CH2CH2-COOCH2CH2-] 2 o R = 3'-tert-butyl-4'-hydroxy-

  2H-benzotriazol-2-yl-phenyl, 2- [2'-hydroxy-3 '- (a, -

  dimethylbenzyl) -5 '- (1,1,3,3-tetramethylbutyl) phenyl] -

  benzotriazole; 2- [2'-hydroxy-3 '- (1.1,3,3-tetramethyl-

  butyl) -5 '- (cL, c-dimethyl-benzyl) phenyl] benzotriazole. 2.2 Hydroxybenzophenones, for example 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy derivatives,

  4-dodecyloxy, 4-benzyloxy, 4,2'4'-trihydroxy, 2'-

hydroxy-4,4'-dimethoxy derivatives.

  2.3. Esters of benzoic acids possibly

- 17 -

  Isubtitus, such as 4-tert-salicylate

  butylphenyl, phenyl salicylate, salicylate

  octyl-phenyl, dibenzoylresorcinol, bis- (4-tert-

  butylbenzoyl) -résorcinol. benzoylresorcinol, 3,5-di-

  2,4-di-tert-butylphenyl tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

  2.4. Acrylates for example x-cyano-5f, -

  ethyl diphenylacrylate, α-cyano-3, -diphenyl-

  isooctyl acrylate. methyl α-carbomethoxycinnamate, methyl acyano-5-methyl-p-methoxycinnamate, α-cyano-3-methyl-methoxycinnamate,

  butyl. Methyl α-carbomethoxy-p-methoxycinnamate.

  N- (D-carbomethoxy-p-cyanovinyl) -2-methylindoline. 2.5, Nickel compounds, for example

  nickel complexes of 2,2'-thio-bis- [4- (1,1,3,3-

  tetramethyl-butyl) -phenol], such as the 1: 1 or 1: 2 complexes, optionally with or without additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyl diethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoesters alkyl, such as, for example, methyl or ethyl ester,

  4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid.

  complexes of nickel with ketoximes, for example 2-

  4-hydroxy-phenylundecylketoxime, nickel complexes with lphenyl-4-lauroyl-5-hydroxypyrazole,

  optionally with additional ligands.

  2.6. Amines with steric hindrance, by

  example sebacate bis (2,2,6,6-tetramethyl-4-

  piperidyl), bis (2,2,6,6-tetramethyl-4-) succinate

  piperidyl), bis (1,2,2,6,6-pentamethyl) -4-sebacate

  piperidyl), bis (1-octyloxy) -2,2,6,6-sebacate

  tetramethyl-4-piperidyl), n-butyl-3,5-di-tert-butyl-

  4-hydroxybenzylmalonate of bis (1,2,6,6,6-pentamethyl)

- 18 -

  4-piperidyl), a condensation product of 1-

  (Hydroxy-ethyl) -2,2,6,6-tetramethyl-4-hydroxypipéri-

  dine and succinic acid, products of

  linear or cyclic condensation of N, N'-

  bis (2,2,6,6-tetramethyl-4-piperidyl) -hexaméthylènedi-

  amine and 4-tert-octyl-amino-2,6-dichloro-1,3,5

triazine, nitrilotriacetate

  tris (2,2,6,6-tetramethyl-4-piperidyl). 1,2,3,4

  tetrakis butane-tetroate (2,2,6,6-tetramethyl-4-

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

  methylpiperazinone), 4-benzoyl-2,2,6,6-tetramethyl-

  piperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine

  dine, 2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) -

  bis- (1,2,2,6,6-pentamethylpiperidyl) malonate, 3-

  n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] de-

  cane-2,4-dione, bis (1-octyloxy) -2,2,6,6-sebacate

  tetramethylpiperidyl), bis (1-octyloxy) succinate

  22,26,6-tetramethylpiperidyl), a condensation product

  cyclic or linear expression of N, N'-bist (2,2,6,6-

  tetramethyl-4-piperidyl) -hexamethylenediamine and 4-morpholino2,6-dichloro-1,3,5-triazine, product

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

  2,2,6,6-tetramethyl-piperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, a product of

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

  1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and

  1,2-bis- (3-aminopropylamino) -ethane, 8-acetyl-3-

  dodecyl-7,7,9,9-tetramethyl-1,3.8-triazaspiro [4.5] -

  decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-

piperidyl) -pyrrolidine-2,5-dione,

  3-dodecyl-l- (1, 2,2,6,6-pentamethyl-4-piperidyl) -

  pyrrolidine-2,5-dione, mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, product

  of condensation of N, N'-bis (2,2,6,6-tetramethyl-4-

  piperidyl) -hexamethylenediamine and 4-cyclohexyl-

  amino-2,6-dichloro-1,3,5-triazine, a condensation product

- 19 -

  of 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine (Register

  CAS n [136504-096-6]), n-dodecylsuccinimide of N-

  (2,2,6,6-tetramethyl-4-piperidyl), n-dodecyl succinic

  mide, N- (1,2,2,6,6-pentamethyl-4-piperidyl), 2-

  undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-

  spiro [4.5] -decane, a reaction product of 7.7.9.9-

  tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxo-

  spiro [4.5] decane and epichlorohydrin, 1.1-

  bis (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2-

  (4-methoxyphenyl) ethene, N, N'-bis-formyl-N.N'-bis-

  (2,2,6,6-tetramethyl-4-piperidyl) -hexaméthylène-

  diamine, diester of 4-methoxy-methylene

  malonic with 1,2,2,6,6-pentamethyl-4-hydroxy-

  piperidine. poly [methylpropyl-3-oxy-4- (2.2.6,6-tetra-

  methyl-4-piperidyl) siloxane, reaction product of the maleic anhydride-α-olefin copolymer with the

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

pentamethyl-4-aminopiperidine.

  2.7. Diamides of oxalic acid, by

  4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxane

  nilide. 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide,

  2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-

  2'-ethyloxanilide. amide of N, N'-bis (3-

  dimethylaminopropyl) oxalic acid, 2-ethoxy-5-tert-butyl-

  2'-ethoxanilide and its mixture with 2-ethoxy-2'-

  ethyl-5,4'-di-tert-butoxanilide, mixtures of methoxy disubstituted oxanilides in ortho and para, mixtures of ortho ethoxy disubstituted oxanilides

and para.

  2.8. 2- (2-Hydrophenol 11-1.3.5-triazine, by

  2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-

  triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis- (2,4-

  dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy)

  phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3., 5-triazine,

- 20 -

  2,4-bis- (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethyl-

  pheny1) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxy)

  phenyl) -4.6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-

  hydroxy-4-dodecyloxy-phenyl) -4., 6-bis (2,4-dimethyl-

  phenyl) -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-butyloxypropoxy) phenyl) -

  4,6-bis (2,4-dimethyl) -1,3,5-triazine. 2- [2-hydroxy-4-

  (2-hydroxy-3-octyloxy-propyl-oxy) -phenyl) -4,6-bis (2,4-

  dimethylphenyl) -1,3,5-triazine. 2- [4- (dodecyl oxy / tri

  decyloxy-2-hydroxypropoxy) -2-hydroxyphenyl-4,6

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

  4- (2-hydroxy-3-dodecyloxy-propoxy) phenyl) -4,6

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

  4-hexyloxy) phenyl) -4,6-diphenyl-1,3,5-triazine, 2- [2-

  hydroxy-4-methoxy) phenyl-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-t (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, for example

* N, N'-Diphenyloxalic acid, N-salicylal-

  N'-salicyloyl hydrazine. N, N'-bis (salicyloyl) -hydra-

  zine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenyl)

  propionyl) -hydrazine, 3-salicyloylamino-1,2,4-

  triazole, dihydrazide of bis (benzylidene) acid -

  oxalic. oxanilide, isophthalic acid dihydrazide, bis-phenylhydrazide acid

  sebacic. dihydrazide of N, N'-diacetyl-

  adipic acid, dihydrazide of N, N'-bis-

  salicyloyloxalic acid dihydrazide, N, N'-bis-

  salicyloyl thiopropionic. 4. Phosphites and phosphonites, eg triphenyl phosphite, diphenylalkyl phosphites,

  phenyldialkyl phosphites, phosphite

- 21 -

  (nonylphenyl), trilauryl phosphite, phosphite

  trioctadecyl, distearyl diphosphite

  erythritol. phosphite tris (2,4-di-tert-butyl-

  phenyl), diisodecylpenta-erythritol diphosphite, diphosphite bis (2,4-di-tert-butyl-

  phenyl) pentaerythritol, diphosphite of bis- (2,6-di-

  tert-butyl-4-methylphenyl) pentaerythritol. diphosphate

  bis (2,4-di-tert-butyl-6-methylphenyl) -pentate

  erythritol, diphosphite bis (2,4,6-tris (tert-

  butylphenyl) pentaerythritol diphosphite. tris triphosphite

  stearyl sorbitol, 4,4'-biphenylenediphosphonite

  tetrakis (2,4-di-tert-butylphenyl) phosphite. 6-isooctyloxy-

  2,4,8.10-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-

  dioxa-phosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-

  12-methyldibenz [d, g] -1,3,2-dioxaphosphocine, phosphite

  bis (2,4-di-tert-butyl-6-methylphenyl) methyl, phos-

  phite of bis (2,4-di-tert-butyl-6-methylphenyl) ethyl,

  phosphite of 2.2 ', 2 "-nitrilo- [triethyl-tris (3,3', 5,5'-

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

  2-ethylhexyl- (3,3 ', 5,5'-tetra-tert-butyl-1,1'-bicarboxyl)

  phenyl-2,2'-diyl). Particularly preferred phosphites are the following: Tris (2,4-di-tert-butylphenyl) phosphite

  (Irgafos 168, Ciba-Geigy), a phosphite of

  (Nonylphenyl), (CH 3) 3 C C (CH 3) 3 (c-3) 3c

C- (A) -CH P-F P-O-CH 2 CH 2 --N (B)

c (CH) 3C

C (C: 3 (C (C33

(CH33C 3

- 4. /. -

(CH3) 3C, C (CH3) 3

O-P-O-CH 2 CH (C 4 H 6) CH 2 CH 3 (C)

(CH3) 3 C

C (CH3) 3

  (CH 3) 3 C (CH 3) C (CH 3) 3 (CH 3) 3 (CH 2)

(CH =) C

C (CH3) 3 (C3C

0 -

HC- C- -CH

O - o p-OCCHCF3 (G)

(F) HC-P, P-O-C C 12

5. Hydroxylamines, for example N, N-

  dibenzyl hydroyclamine. N, N-diethylhydroxylamine, N, N-

  dioctyl hydroxylamine, N, N-dilaurylhydroxylamine, N.N-

  ditertra-decylhydroxylamine, N, N-dihexadecylhydroxyl

  amine, N, N-dioactadecylhydroxylamine, N-hexadecyl-N-

  octadecyl-hydroxylamine, N-heptadecyl-N-octadecyl-

  hydroxylamine, N, N-dialkyhydroxylamine derived from a

hydrogenated fatty amine.

  6, Nitrones, for example N-benzyl-alpha-

  phenyl-nitrone. N-ethyl-alpha-methyl-nitrone, N-octyl-

  alpha-heptyl-nitrone. N-lauryl-alpha-undecyl-nitrone.

- 23 -

  N-tetradecyl-alpha-tridecyl-nitrone, N-hexadecyl-

  alpha-pentadecyl-nitrone, N-octadecyl-alpha-hepta-

  decyl-nitrone, N-hexadecyl-alpha-heptadecyl-nitrone,

  N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecyl-

  alpha-heptadecyl-nitrone, N-octadecyl-alpha-penta-decyl-nitrone, N-heptadecyl-alpha-heptadecyl-nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N, N-dialkylhydroxylamine derived from an amine

hydrogenated fat.

  7. Thiosynergistic, for example thiody

dilauryl propionate or

distearyl thiodipropionate.

  8. Peroxide destroyers, for example esters of othiodipropionic acid, for example lauric, stearic, myristic or tridecyl esters, mercaptobenzimidazole or zinc salt of 2-mercapto-benzimidazole, dibutyldithiocarbamate

  zinc, dioctadecyl disulfide, tetrakis (5-

  dodecylmercapto) pentaerythritol propionate, 9. Basic costabilizers, eg melamine, polyvinylpyrrolidone, dicyanodiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal and alkaline earth metal salts higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate. 10. Nucleating agents, for example inorganic substances, such as talc, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals composed of organic, such as mono- or

  polycarboxylic acids and their salts, for example, 4-

- 24 -

  tert-butylbenzoic. adipic acid, diphenyl

  acetic acid, sodium succinate or sodium benzoate polymeric compounds, such as ionic copolymers (ionomers). 11. Fillers and reinforcing agents, eg calcium carbonate, silicates, fiber

  glass, glass beads, asbestos, talc, kaolin, mica.

  barium sulphate, oxides and hydroxides of metals, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers. 12. Other additives, eg plasticizers, lubricants, emulsifiers, pigments, rheology additives, catalysts, thinners, optical brighteners, flame retardants. antistatic agents and blowing agents. 13. Benzofuranones and indolinones, for example those disclosed in the patents

  U.S. 4,325,863; U.S. 4,338,244 U.S. 5,175,312:

  U.S. 5,216,052: U.S. 5,252,643 to 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-stearyl)

  oxyethoxy) phenyl] -benzofuran-2-one, 3,3'-bis [5,7-di-

  tert-butyl-3- (4- (2-hydroxyethoxy) phenyl] benzofuran-2-

  one, 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran

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

  butylbenzofuran-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-butylbenzofuran-2-one, 3-

  (2,3-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-

  one. The costabilizers, with the exception of the benzofuranones mentioned in point 13, are added in concentrations of, for example, 0.01 to 10%, by

- 25 -

  in relation to the total weight of the polyamide, polyester or

polyacetal to stabilize.

  Other preferred compositions comprise other additives in addition to components (a) and (b), in particular phenolic antioxidants, light stabilizers and / or processing stabilizers. Particularly preferred additives are phenolic antioxidants (point 1 of the list), sterically hindered amines (point 2.6 of the list), phosphites and phosphonites (point 4 of the list) and peroxide scavengers (point 8 of the list). listing). Particularly interesting compositions are those which comprise in addition to components (a) and (b) as another additive at least one compound of the phosphite or organic phosphonite type (point 4 of

the list).

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

  U.S. 4,325,863 U.S. 4,338,244; U.S. 5,175,312;

  U.S. 5,216,052 U.S. 5,252,643, DE-A-4,316,611,

  DE-A-4,316,622, DE-A-4,316,876; EP-A-0 589 839 or EP

A-0 591 102.

  Examples of such benzofuran-2-ones are compounds of the formula: R'15

R '12H

- 26 -

  wherein pi represents a substituted or unsubstituted heterocyclic or carbocyclic aromatic ring system R12 represents a hydrogen atom; R14 represents a hydrogen atom. alkyl groups of 2 to 12 carbon atoms, cyclopentyl. cyclohexyl or chloro R13 has the meaning of R12 or R14 or

O

  It represents a radical of formula - (CH2) -C-OR'16 O o o Il Il Il

  - (CH 2), C-N (R ', 7) 2 .- (CH), C-O-A-O-C- (CH), - E.

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

O O O

  ## STR2 ## wherein R 16 is a CH 2 Cl 2 (CH 2) 2 CH 3 (CH 2) n, CH 2 Z 2 R 9, CH 6 C 6 H 6 hydrogen atom. alkyl groups with 1 to 18 carbon atoms: alkyl with 2 to 18 carbon atoms which is interrupted by oxygen or sulfur atoms, dialkylaminoalkyl containing a total of 3 to 16 carbon atoms, cyclopentyl, cyclohexyl. phenyl or phenyl substituted with 1 to 3 alkyl radicals containing together not more than 18 carbon atoms s is 0, 1 or 2 R17 the R17 substituents each independently of one another represent a hydrogen atom, alkyl groups with 1 to 18 carbon atoms, cyclopentyl, cyclohexyl,

- 27 -

  phenyl, phenyl which is substituted with 1 or 2 alkyl radicals not containing together more

  of 16 carbon atoms, a radical of formula -

C2H4OH.

O

  -C2H4-O-CtH2t + 1 or -C2H-C-R'U or together with the nitrogen atom that connects them, form a piperidine radical or a morpholine radical: t ranges from 1 to 18 R20 represents a hydrogen atom, alkyl groups with 1 to 22 carbon atoms or cycloalkyl with 5 to 12 carbon atoms: A represents an alkylene group with 2 to 22 carbon atoms, which may be interrupted by a nitrogen atom, a oxygen or sulfur R18 represents a hydrogen atom, alkyl groups with 1 to 1 carbon atoms, cyclopentyl, cyclohexyl, phenyl; phenyl or benzyl groups substituted by 1 or 2 alkyl radicals together containing not more than 16 carbon atoms; R19 represents an alkyl group with 1 to 18 carbon atoms;

  D represents -O-, -S-, -SO-, -SO2- or -C (R21) 2-

  R21 substituents R21 are each independently of one another a hydrogen atom or a C1-C16 alkyl group, the two substituents R21 containing together from 1 to 16 carbon atoms, R21 being also a group phenyl or a radical of formula

O O

He 11

- (CH2) C-OR16 OR -CH2) C-N (R'17) 2

SHou) 17) 2 or II

  R16 and R17 have the meanings cited above.

above;

- 28 -

E represents a radical of formula

R '15

R'14 0

/ Cs

R'12 H

o

  Rl1, R12 and R14 have the meanings cited above.

  above; and R15 represents a hydrogen atom ,. alkyl groups with 1 to 20 carbon atoms, cyclopentyl. cyclohexyl, chloro or a radical of formula

O O

  II - (CH2) '- C-OR'16 or - (CH2) - "CN (R'17) 2, where R16 and R17 have the meanings mentioned above, or R15, together with R14, is a tetramethylene radical, benzofuran-2-ones, R13 represents a hydrogen atom, alkyl groups with 1 to 12 carbon atoms, cyclopentyl, cyclohexyl, chlora or a radical of formula

O O

  -CH - C-OR16 or -C-N (R'17) 2 'or -D-E, o

  s, R1, R17, D and E have the meanings cited above.

  R1l is preferably a hydrogen atom, alkyl groups with 1 to 18 carbon atoms,

cyclopentyl or cyclohexyl.

  Other preferred benzofuran-2-ones are those

- 29 -

  R 11 is a phenyl or phenyl group which is substituted with 1 or 2 alkyl radicals containing not more than 12 carbon atoms R 12 represents a hydrogen atom; RI4 represents a hydrogen atom or an alkyl group with 1 to 12 carbon atoms; R13 represents a hydrogen atom, an alkyl group with 1 to 12 carbon atoms,

O O

  It is t - (CH 2) -C - OR '16, -C - H2 - C - N (R' 17) 2 or - D - E; R15 representing a hydrogen atom, an alkyl group or II with 1 to 20 carbon atoms, -aCHuC-OR16 or

O

  II - (CH2) C N (R'17) 2, or R'15, together with 14. repreenting a tetramethylene radical, s,

! I

  R16, R17, D and E having the meanings

data in the description.

  Particularly interesting benzofuran-2-ones are also those in which R13 represents a hydrogen atom, an alkyl group

I I

  with 1 to 12 carbon atoms or -D-E; R12 and R14 are each independently of one another a hydrogen atom or an alkyl group with 1 to 4 carbon atoms; and R 15 represents an alkyl group with 1 to 20 carbon atoms, D and E having the

  meanings given in the description.

  Finally, a particular interest is also represented by those of benzofuran-2-ones, where R 13 represents an alkyl group with 1 to 4 carbon atoms or D-E; R12 and R14 represent a hydrogen atom and R15 represents alkyl groups

- 30 -

  with 1 to 4 carbon atoms, cyclopentyl or cyclohexyl, D being -C (R21) 2 and E being a radical of formula

R '15

R 14 O

IR'1

R'12 H "

  the substituents R 21 are identical or different and each represents an alkyl group with 1 to 4 atoms

II II

  carbon, and R11, R12, R14 and R15 have the

given meanings.

  The amount of benzofuran-2-ones additionally added may vary within wide limits and may be present in the compositions of the present invention in an amount of, for example, 0.0001 to 1% by weight, preferably 0.001 to 2%. in weight,

  particularly preferably from 0.01 to 2% by weight.

  Component (b) and optionally other additives are incorporated in component (a) [polyamide, polyester or polyacetal] according to known methods, for example before or after molding, or also by application of component (b) dissolved or dispersed on the component (a) with or without subsequent evaporation of the solvent. Component (b) may also be added to the materials to be stabilized [component (a)] in the form of a masterbatch which contains these components in a

  concentration for example 2.5 to 25%.

  Component (b) can also be added before

  or during the polymerization or before the crosslinking.

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

- 31 -

  polymers. The component (b) can also be sprayed on the component (a) to be stabilized. It is capable of diluting other additives (for example the conventional additives listed above) or their mixtures, so that they can be sprayed together

  with these additives on the component (a) to be stabilized.

  Spray addition during the inactivation of the polymerization catalysts is particularly advantageous since it is possible to spray using

  for example, the steam used for inactivation.

  The polyamides, polyesters or polyacetals thus stabilized can be used in a very large number of different forms, including

  characteristic of films, fibers, filaments.

  molded articles, profiles, or as binders for paint systems, particularly powder coating compositions, for

adhesives and sealants.

  Component (b) is particularly suitable for use as a processing stabilizer (thermal stabilizer). For this purpose, it is particularly useful to add the component (a)

  before or during implementation.

  Therefore, a preferred embodiment of the present invention is the use of component (b) as a stabilizer, in particular as an implementation stabilizer (thermal stabilizer), for the stabilization of polyamides, polyesters or polyacetals against oxidative degradation , thermal

and / or induced by light.

  Component (b) is characterized by its advantageous color fastness, that is to say low discoloration of polyamides, polyesters and polyacetals during the course of

implementation.

- 32 -

  Therefore, this invention also relates to a method for stabilizing a polyamide, a polyester, or a polyacetal against oxidative, thermal, and / or light-induced degradation, which process comprises incorporating into, or the application to. said material of at least one

component (b).

  The following examples illustrate the invention in more detail, Parts and percentages

are expressed by weight.

  Example 1 Stabilization of Polyamide 12

  100 parts of unstabilized polyamide 12 granules (GrilamidL20 G. from EMS, Switzerland) were crushed by cryogenic grinding and stabilizers listed in Table 1 were charged. This mixture was mixed in a Henschel mixer for 2 minutes at room temperature. C. The powder thus obtained is then dried at 80 ° C. for 6 hours and then extruded in a twin screw extruder (Berstorff type) at a temperature of

  maximum temperature of 210 C and then granulated.

  The granules obtained in an injection molding apparatus (Engel type) are molded by injection at a maximum temperature of 220 ° C. to obtain dumbbells. The yellowness index (YI) of these dumbbells is determined according to ASTM D 1925-70. Low YI values indicate low discoloration, high YI values indicate strong discoloration of the samples. The less discoloration there is, the more effective the stabilizer or stabilizing mixture. The results are

collected in Table 1.

(See table 1 next page)

- 33 -

Table 1:

  Example Stabilizer Yellowing index (dumbbells) laa) 6.7 lba) 0.25% Irganox @ 245c) 8.9 lcca) 0.50% IrganoxJ245C) 9.6 ica) 0.25% Irganoxl1098d) 9.2 ida) 0.50% Irganox 1098d) 10.7 lfb) 0.25% component (b) e) 6.3 lgb) 0.50% component (b) e) 6.4 0.25% Irganox245c) f lha) 0.25% Irgafost168f) 6.8 ia) 0.25% Irganox @ 1098d) 7.6 l) 0.25% Irgafos $ 168f) 0.25% component (b) e) ljb) 0.25% Irgafos1l68f) 5,7 _ka) 0,25% Irganox9245C) 5,3 __ _ 0,25% Irgafos1l2g) 5 0,25% Irganox 1098d) la) 0,25% Irgafosl2g) 6 0,25% component (b) e) mb 0.25% Irgafosl2g) 3 a) Comparative Example b) Example of the present invention c) Irganox® 245 (Ciba Spezialitätenchemie AG) represents a compound of formula AO-1

3C \ H H3C HCH3

  ## STR2 ## ## STR4 ## ## STR2 ##

CH3 CH3

  d) Irganox31098 (Ciba Spezialitâtenchemie AG) represents a compound of formula AO2

- 34 -

HC CH3

3 \, CH3C CH3

C 0 0 - CH3

H3C__il I OH

  CH 2 CH 2 CH 2 C-NH- (CH 2) p NHC-CH 2 -CHH (AO 2) H 3 C-. / -.

C "CH3

  / CH3 e) Component (b) is a compound of formula I '

HO IHCH, CH3

H3C \ .C 00C

  CH2-CH1-C-NH- (CH2) i-NH-C-CHrCH2-OH

CH3 CH3

  Irgafos0158 (CibeSpazialitâtenchemieAG)

  represents the phosphite of tris (2,4-di-tertiary

  butylphenyl). g) Irgafos @ 12 (Ciba SpezialitätenchemieAG)

  represents the phosphite of 2,2 ', 2 "-nitrilo-

  [Triethyl-tris (3,3 ', 5,5'-tetra-tert-butyl-1,1'-

  biphenyl-2,2'-diyl)]; Chemical Abstract Registry Number 80410-33-9, and represents the compound of formul13

30

  Example 2 Stabilization of polyamide 6

- 35 -

  100 parts of stabilized polyamide 6n granules (Ultramid3B3S, from BASF) were crushed by cryogenic grinding and loaded with the stabilizers listed in Table 2. This mixture was then mixed in a Henschel mixer for 2 minutes at C. Dry the powder thus obtained at a temperature of 80 ° C. for 6 hours and extruded in a twin-screw extruder (Berstorff type) at a temperature of

  maximum temperature of 240 C and then granulated.

  The injection-produced granules are molded in an injection molding apparatus at a maximum temperature of 240 ° C. to obtain small rods 4 × 6 mm thick and 50 mm long. These rods are then aged in an oven at 150 ° C. with recirculation of air. The time required for the resistance of the rods to fall to 80 kJ / m2 is measured in hours. The longer the time, the better the stabilization. The results are

collected in Table 2.

  Table 2: Impact resistance in the oven aging test at 150 C Stabilizing Time in hours at Example 150 C until the impact resistance reaches KJ / cm2 2aa) 2 2ba) 0.25% Irganox 245c) 28 2ca) 0.25% Irganox 1098d) i 30 2db) 0.25% component (b) e) l See footnote a) to e) for explanations at the end of Table 1 Example 3: Stabilization of polyoxymethylene copolymer (POM) 100 parts of non-POM copolymer are mixed

- 36 -

  stabilized (HostaformC, Hoechst) with 0.3% calcium stearate and with the stabilizers indicated in Tables 3, 4 and 5. The powder is then extruded at a maximum temperature of 190 C. Part of these granules are molded by injection into an injection molding apparatus at a maximum temperature of 200 C into wafers 2 mm thick, mm wide and 60 mm long. The other portion of the granules is injection molded in an injection molding apparatus at a maximum temperature of C into small sticks 4 x 6 mm thick.

and 50 mm in length.

  The thermogravimetric measurements are carried out isothermally on a part of these platelets under an air flow of 220 C. The minutes are measured in minutes at the end of which the platelets lose 3%. 6% and 10% of their weight. The longer the time, the better the stabilization. The results are gathered in

Table 3.

  Table 3: Thermometric Measurements at 220 C Time in minutes flowing to Example Stabilizing weight loss

3% 6% 10%

  3a) 0.30% Irganox 245c) 53 70 88 3ba) 0.30% Irganox (1098d) 78 103 127 3Cb) 0.30% compound (b) 82 114 157 See footnote a) ae) at the end of Table 9 For explanation on another example of an acate, an aging test is carried out in an air recirculating oven 140 IC and the time at which the platelets lose 2% of the product is measured in hours. their weight. The longer the time, the better the stabilization. The

  The results are summarized in Table 4.

  Table 4 Weight loss in the oven aging test at 140 C Time in hours Example Stabilizer at the end of which the weight loss is 2% 3da) 0.30% Irganox245c) 1300 3ea) 0.30% Irganox11098d ) 2150 3fb) 0.30% component (b) e) 2700 See footnote a) through e) for explanations at the end of Table 1. The sticks are also 4 x 6 mm thick and from 50 mm in length to an aging test at 140 C in the air recirculating oven, measuring in hours the time required for the impact resistance to fall from 110 kJ / m2 to kJ / m2. The longer the time, the better the stabilization. The results are gathered in the

Table 5.

  Table 5 Impact resistance in the oven aging test at 140 C Time in hours at Example Stabilizer 140 C until impact resistance of 90 KJ / cm 2 2ga) 0.30% Irganoxd245c ) 770 2ha) 0.30% Irganox @ 1098d) 800 2ibirqe 1250 ______ 0.30% cc_ _osa_ _ (bel See at the end of Table 1 footnotes a)

to e) for explanations.

- 38 -

Claims (11)

REVENDI CATIONS   A composition which comprises: a) a polyamide, a polyester or a polyacetal which is subjected to oxidative, thermal or light-induced degradation, and b) a ccrmoss of formula HO C H3 H3C \ / OH3 CH H0, uO - / CH3   HO È: H2 CH2C NH (CH2) 22H-H2 O4H (1L) CH3 CH3   provided that if component (a) is a polyamide, then the composition does not contain metal hypophosphite or copper salt of a organic acid. 2. Composition according to the   cation 1, where the polyamide is polyamide 6, polyamide 6.6, polyamide 4.6, polyamide 11 or   polyamide 12 or a copolymer thereof. 3. Composition according to the   cation 1, wherein the polyester is PET, PETG or PBT or a copolymer thereof. 4. Composition according to the   cation 1. in which the polyacetal is a homopolymer or a copolymer. 5. Composition according to the   cation 1, wherein the compound (b) is present in an amount of 0.01 to 1% based on the weight of the compound (a). 6. Composition according to the   cation 1, which additionally comprises other additives alongside compounds (a) and (b). 7. Composition according to the   cation 6, wherein the other additives are phenolic antioxidants, stabilizers at _ 39 _   light and / or stabilizers implementation. 8. Composition according to the   cation 6. in which the additional additive is at least one compound of the phosphite or organic phosphonite type. 9. Composition according to the   in which the additional additive is   at least one compound of the benzofuran-2-ones type.   10. Process for the stabilization of a polyamide of a polyester or polyacetal against oxidative degradation. thermal and / or light induced, which comprises incorporation into, or application to. said materials on at least one   component (b) according to claim 1.   11. Use of component (b) according to claim 1 as a stabilizer for the protection of polyamides, polyesters or polyacetals against oxidative degradation,   thermal, and / or induced by light.