GB2311528A - Stabiliser mixtures for polyamides, polyesters and polyketones - Google Patents

Description

2311528 Stabilisation of polyamide, polyester and poiyketone The present

invention relates to compositions comprising a polyamide, polyester or polyketone, a specific organic phosphite (1rgafos12, Ciba- Geigy) and a sterically hindered phenol, to the use thereof for stabilising polyamide, polyester or polyketone against oxidative, thermal andlor light-induced degradation, as well as to a process for stabilising these plastic materials.

It is known from U.S. patent 4 360 617 that stabiliser mixtures comprising symmetrical triarylphosphites and specific phenolic antioxidants are particularly suitable for protecting specific organic materials, such as polyurethane, polyacrylonitrile, polyamide 12 or polystyrene, from oxidative, thermal or light-induced degradation. Tris(2, 4-di-tert-butylphenyi)phosphite (1rgafos168, Ciba-Geigy) is disclosed as the preferred triaryl phosphite.

In polyamides, polyesters and polyketones, these known stabiliser mixtures cannot meet all the demands made on them. It is known that such stabiliser mixtures reduce the starting colour as well as the colour development of the polyamide during oven ageing and that they reduce the decrease of the mechanical properties of the polyamide during oven ageing and exposure to light. A disadvantage of these stabiliser mixtures is that it is often found that these phosphites have a tendency to bloom.

U.S. Patents 4 318 845 and 4 374 219 disclose alkanolamine esters of cyclic 1,1'-biphenyl2,2'-diy] phosphites and alkylidene-1,1'-biphenyi-2, 2'-diyl phosphites as stabilisers for organic polymers and lubricating oils, especially as processing stabilisers for polyolefins, elastomers, polyesters and polycarbonates.

It has now been found that a stabiliser mixture comprising a very specific phosphite, selected from the U.S. patents 4 318 845 and 4 374 219, together with a very specific group of sterically hindered phenols, is particularly suitable as stabiliser for polyamides, polyesters or polyketones. The polyamides, polyesters or polyketones thus stabilised have enhanced properties with respect to oxidative, thermal andlor lightinduced degradation, and the novel phosphite does not bloom.

Accordingly, this invention relates to compositions, comprising a) a polyamide, polyester or polyketone which is subject to oxidative, thermal or lightinduced degradation, b) the phosphite of formula 1 (CH3)3C C(CH 0 X / P-O-CH2CHi-N 0 (CHIC C(CHI 3 and c) at least one compound of formula 11 H3C \ ",CH3 H3C L HOR1X Tn R2 wherein R, is Cl-C4alkyl, n is 1, 2, 3 or 4, 0 0 11 H Xismethylene, -CHI---CH--,.,-y- or -CH-,,,-u-kHI--CH, Y is oxygen or -NH-; and, if n = 1, 0 11 X is -CHi--CHi-C-Y- wherein Yis boundto R2, and R2 is Cl-C25alkyl; and, if n = 2, 0 X is -CHi--,n 2 G- T wherein Y is bound to R2, and R2 is C2-C12alkyiene, C4-CI2alkylene which is interrupted by oxygen or sulfur; or, if Y is -NH-, R2 is additionally a direct bond; and, if n = 3, 0 11 X is methylene or -CHi-t,-u-kHi--CHi--wherein the ethylene group is bound to R2, and 1 R2 is Y and, N Y N 0 if n = 4, 0 X is -CH2 Cri 2 C- v'-, wherein Y is bound to R2, and R2 is C4-Cloalkanetetrayl.

Alkyl of up to 25 carbon atoms is a branched or straight-chain radical, typically methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethyibutyi, n-pentyl, isopentyl, 1 methylpentyi, 1,3dimethyibutyi, n-hexyi, 1-methylhexyl, n-heptyl, isohepty], 1,1,3,3tetramethylbutyl, 1-methy[hepty], 3-methylheptyl, n-octyi, 2-ethylhexyl, 1,1,3-trimethyihexyi, 1,1,3,3- tetramethylpentyl, nonyl, decyl, undecyl, 11-methylundecyl, dodecyl, 1,1, 3,3,5,5-hexamethyihexyi, tridecyl, tetradecyl, pentadecyi, hexadecyl, heptaclecyl, octadecyi, eicosyl or docosyl. Preferred meanings of R, are methyl and tert-butyl. R2 is particularly preferably ClC20alkyl, especially Cl-Claalkyl, typicallyC4-Clgaiky]. R2 is particularly preferably C8-C18alkyl, especially C 14-Claalkyi, typically C18-alky].

C2-Cl2Alkylene is a branched or straight-chain radical, typically ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene or dodecamethylene. R2 is particularly preferably e.g. C2-Cloalkylene, especially C2-C8alkylene. R2 is particularly preferably e.g. C4-C8alkylene, especiallY C4-C6-alkylene, typically hexamethylene.

C4-C12Alkylene which is interrupted by oxygen or sulfur can be interrupted once or several times and is typically -CH2-0-CH2CH2-0-CH2-, CH2-(0-CH2CH2-)20-CH2-, -CH2-(O-CH2CH2)30-CH2-, -CH2-(0-CH2CH2-)40-CH2-, -CH2CH2-0-CH2CH2-0- CH2CH2- or -CH2CH2-S-CH2CH2-. R2 is particularly preferably e.g. C4- Cloalkylene which is interrupted by oxygen or sulfur, especiallyC4- C8alkylene which is interrupted by oxygen or sulfur, typically C4- C6alkylene which is interrupted by oxygen or sulfur. R2 is particularly preferably -CH2CH2-0-CH2CH2-0-CH2CH2- or -CH2CH2-S-CH2CH2-.

CH- Alkanetetrayl of 4to 10 carbon atoms is typically -CH2 C-CH2 (pentaerythritol), i CHi-- -CH2 CH-CH-CH2 -CH-CH 2 CH-CH-CH 2 or -CH2 CH2 CH-CH-CH2 CH2 -CH2 CH2 CH2 Pentaerythritol is preferred. -CH2 CH2 CH-CH2 um-uti-uH2 CHj- Component (c) can also be mixtures of different sterically hindered phenols of formula 11.

Interesting compounds are those containing as component (c) at least one compound of formula 11, wherein, if n = 1, R2 is Cl-C20alkyl.

Preferred compositions are those containing as component (c) at least one compound of formula 11, wherein, if n = 2, R2 is C2-C8alkylene, C4-C8alkylene which is interrupted by oxygen or sulfur; or, if Y is -NH-, R2 is additionally a direct bond and, if n = 4, R2 is C4-C8alkanetetrayl.

Preferred compositions are also those containing as component (c) at least one compound of formula 11, wherein, R, is methyl or tert-butyl, n is 1, 2 or 4, 0 X is -Cri:F-Cri 2 C-v- Y is oxygen or -NH-; and, if n = 1, R2 is C14-C1,9alkyl; and, if n = 2, R2 is C4-C6alkylene, or C4-C6alkylene. which is interrupted by oxygen; and, if n = 4, R2 is C4-C6alkanetetrayl.

Interesting compositions are also those containing as component (c) at least one compound of formula 1, wherein the compound of formula 1 is a compound of formula lia to 11h H3C \,CH 3 H3C 0 HO CH2 CHi-C-NII-(CH2)3 (lia), Irganox"1098 H3C -, c H3C / CH3 -2 HC \ 1C113 H3C 0 11 HO CHi-CH:F-C-O-Cl.H37 (lib), Irganox1076 H3c-- c H3C / CH3 H C \ ',CH3 H3C 0 11 HO CHi--CHF--C-O-CHi---C (lic), Irganox"1010 H3C -- c H3C / CH 3 4 H3C \,CH 3 H 3C 0 HO (lid), Irganox245 CHi--CHi---C-u-krli--CHi--0-CH 2 H 3C 12 3 CH3 H3C 0 11 HO CHi--CH:--C-O-(CH (fie), Irganox259 H3C -, c H3C / CH3 H 3C CH H3C 0 HO -CHi----CHi----C-O-(CH 2)- S (11% frganox1035 H3c-, H3C / CH3 R H C CH3 3 3 1 c 0 N 0 CH 3 y R CH OH N N, 3 2 -0i-' (fig), Irganox'3114 3 y 3." C H H 3C \ CH 3 R3 H3C 11 c CH3 1 0 1\ 0 N 0 CH3 Y R3 (CH2C 0 - C - CH2-C 0 H (11h), Irganox3125.

N N, R R3 CH 3 Y H3C CH 3 Irganox"1098, Irganox1076, Irganox31010, Irganox"245, Irganox0259, Irganox"3114, Irganox1035 and Irganox3125 are trademarks of Ciba-Geigy.

Preferred compositions are those containing as component (c) at least one compound of formula 1, wherein the compound der formula 1 is a compound of formula lia, lib, lic or Ild, in particular a compound of formula lia, lib or lic, typically a compound of formula lla.

Component (b) of the novel composition, or the phosphite of formula 1, is known and its preparation is disclosed in Example 4 of U.S. patents 4 318 845 and 4 374 219 mentioned at the outset. This phosphite can be obtained in different modifications, as disclosed, inter alia, in the following U. S. patents. U.S. 5 276 076 discloses a solid amorphous form of the phosphite of formula 1. U.S. 5 334 739 discloses the cc-crystalline form of the phosphite of formula 1. U.S. 5 326 802 discloses the 0-crystalline form, and U.S. 5 321 031 discloses the -y-crystailine form, of the phosphite of formula 1. The phosphite of formula 1 is commercially available under the trademark Irgafoss12 (Ciba-Geigy).

Component (c) of the novel composition, or the compounds of formula 11, are known and some are commercially available. Possible processes for the preparation of the compounds of formula 11 may be found, inter alia, in U. S. patents 3 330 859 and 3 960 928.

Polyamides will be understood as meaning aliphatic and aromatic polyamides or copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or their corresponding lactams. Suitable polyamides are, for example: PA 6, PA 11, PA 12, PA 46, PA 6.6, PA 6.9, PA 6.10 or PA 6.12, PA 10. 12, PA 12.12 and also amor- phous polyamides of the Trogamid PA 6-3-T and Grilamid TR 55 type. Polyamides of the cited type are commonly known and are commercially available.

Interesting compositions are those containing as component (a) polyamide 6, polyamide 6.6, polyamide 11 or polyamide 12 or copolymers thereof, in particular polyamide 6 or polyamide 6.6, or elastomer-modified polyamide 6 or polyamide 6.6 blended with polypropylene.

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

The aliphatic dicarboxylic acids may contain 2 to 40 carbon atoms, the cycloaliphatic dicarboxylic acids may contain 6 to 10 carbon atoms, the aromatic dicarboxylic: acids may contain 8 to 14 carbon atoms, the aliphatic hydroxycarboxyiic acids may contain 2 to 12 carbon atoms, and the aromatic as well as the cycloaliphatic hydroxycarboxylic acids may contain 7 to 14 carbon atoms.

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

Aromatic diols are those, wherein two hydroxyl groups are bound to one or different aromatic hydrocarbon radicals.

It is also possible that the polyesters are branched with small amounts, e.g. from 0.1 to 3 mol%, based on the dicarboxylic acids present, of more than difunctional monomers (e.g. pentaerythritol, trimellitic acid, 1,3,5tri(hydroxyphenyl)benzene, 2,4-dihydroxybenzoic acid or 2-(4hydroxyphenyi)-2-(2,4-dihydroxyphenyl)propane).

In polyesters consisting of at least 2 monomers, these can be randomly distributed or may be block copolymers.

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

Aliphatic dicarboxylic acids are suitably those containing 2 to 40 carbon atoms, typically oxalic acid, malonic acid, dimethyimalonic acid, succinic acid, pimelic acid, adipic acid, trimethyiadipic acid, sebacic acid, azelaic acid and dimeric acids (dimerisation products of unsaturated aliphatic carboxylic acids such as oleic acid), alkylated malonic and succinic acids such as octadecyisuccinic acid.

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

Suitable aromatic dicarboxylic acids are: Preferably terephthalic acid, isophthalic acid, ophthalic acid as well as 1,3-, 1,4-, 2,6- or 2,7naphthalenedicarboxylic acid, 4,4'-diphenyidicarboxylic acid, 4,4'diphenyisuifonedicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 1,1, 3-trimethyi-5-carboxyl-3-(p-carboxylphenyi)indane, 4,4'-diphenyl ether dicarboxylic acid, bis-p(carboxylphenyi)methane, or bis-p(carboxylphenyi) ethane.

The aromatic dicarboxylic acids are preferred and of these, in particular, terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid.

Further suitable dicarboxylic acids are those containing -CO-NH groups; they are disclosed in DE-A-2 414 349. Dicarboxylic acids containing Nheterocyclic rings are also suitable, for example those which are derived from carboxylalkylated, carboxylphenylated or carboxybenzylated monoamines-triazinedicarboxylic acids (see DE-A-2 121 184 and 2 533 675), mono- or bishydantoins, benzimidazoles which may be halogenated, or parabanic acid. The carboxyalkyl groups can in this case contain 3 to 20 carbon atoms.

Suitable aliphatic diols are the linear and branched aliphatic glycols, preferably those of 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-butanediol, pentyl glycol, neopentyl glycol, 1, 6hexanediol, 1,12-dodecanediol. A suitable cycloaliphatic diol is, for example, 1,4-dihydroxycyclohexane. Further suitable aliphatic diols are typically 1,4-bis(hydroxymethyl)cyclohexane, aromatic-aliphatic diols, such as p-xylylene glycol or 2,5-dichloro-p-xylyiene glycol, 2,2-(0hydroxyethoxyphenyi)propane as well as polyoxyalkylene glycols, such as diethylene glycol, triethylene glycol, polyethylene glycol or polypropylene glycol. The alkyienediols are preferably linear and preferably contain 2 to 4 carbon atoms.

Preferred diols are the alkylenediols, 1,4-dihydroxycyciohexane and 1,4bis(hydroxym ethyl)cyclohexane. Ethylene glycol, 1,4-butanediol as well as 1,2- and 1,3-propylene glycol are particularly preferred.

Further suitable aliphatic diols are the 0-hydroxyalkylated, preferably 0hydroxyethylated, bisphenols such as 2,2-bis[4'-(0hydroxyethoxy)phenyllpropane. Further bisphenols as indicated later.

Another group of suitable aliphatic diols are the heterocyclic diols disclosed in the German specifications 1 812 003, 2 342 432, 2 342 372 and 2 453 326. Illustrative examples are: N, N'-bis(p-hyd roxyethyi)-5,5- di methyl hydantoi n, N,N'-bis(p-hydroxypropyi)-5,5-dimethyl-hydantoin, methylenebis[N-(0-hydroxyethyf)-5-methyi-5-ethyihydantoinj, methylenebis[N-(0-hydroxyethyi)-5,5-dimethyihydantoin], N,N'-bis(ohydroxyethyl)benzimidazolone, N,W-bisffl-hyd roxyethyl)-(tetrach lo ro) ben zi m idazo lone, or N,N'-bis(p-hydroxyethyi)(tetrabromo)benzimidazolone.

Suitable aromatic diols are mononuclear diphenols and, preferably, binuclear diphenols, which carry a hydroxyl group at each aromatic nucleus. Aromatic will preferably be understood as meaning aromatic hydrocarbon radicals such as phenylene or naphthylene. In addition to, for example, hydroquinone, resorcinol or 1,5-, 2,6- and 2,7dihydroxynaphthalene, those bisphenois merit particular mention which can be illustrated by the following formulae:

R' R, R' R, HO OH HO HO R' R, R' R' HO OH O-A-0-A--0 W. W' R' R' HO OH O-A-0-0-A-- W' R' R' R' HOO_A A A--t OH R' R' R' R' HO OH W R' The hydroxyl groups can be in m-position, preferably in p-position, R' and W in these formulae may be alkyl of 1 to 6 carbon atoms, halogen such as chloro or bromo and, preferably, hydrogen atoms. A can be a direct band, or oxygen, sulfur, -SO-, -S02-, "C=0 11 -P(O)(CI-C2oalkyi)-, unsubstituted or substituted alkylidene, cycloalkylidene or alkylene.

Typical 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, trichforoethylidene.

Typical examples of unsubstituted or substituted alkylene are methylene, ethylene, phenylmethylene, diphenyimethylene, methylphenyimethylene. Typical examples of cycloalkylidene are cyclopentylidene, cyciohexylidene, cycloheptylidene and cyclooctylidene.

Illustrative examples of bisphenols are: bis(p-hydroxyphenyi)ether or bis(p-hydroxyphenyl)thioether, bis(p-hydroxyphenyi)suifone, bis(phydroxyphenyi) methane, bis(4-hydroxyphenyl)-2,2'-biphenyl, phenylhydroquinone, 1,2-bis(p-hydroxyphenyi)ethane, 1 -phenylbis(phydroxyphenyi)methane, diph enyl-bis(p-hyd roxyphenyl) methane, diphenyi-bis(p-hydroxyphenyl)ethane, bis(3,5-dimethyi-4hydroxyphenyi)suifone, bis(3,5-dimethyi-4-hydroxyphenyi)-pdiisopropyibenzene, bis(3,5-dimethyi-4-hydroxyphenyi)-mdiisopropyibenzene, 2,2bis(3',5'-dimethyi-4'-hydroxyphenyi)propane, 1,1 or 2,2-bis(p-hydroxyphenyi)butane, 2,2bis(phydroxyphenyi)hexafluoropropane, 1,1 -dichloro- or 1,1,1 -trichloro-2,2bis(p-hydroxyphenyl)ethane, 1, 1 -bis(p-hydroxyphenyl)cyclopentane and, preferably, 2,2-bis(p-hydroxyphenyl)propane (bisphenol A) and 1,1-bis(phydroxyphenyl)cyclohexane (bisphenol C).

Suitable polyesters of hydroxycarboxylic acids are typically polycaprolactone, polypivalo- lactone or the polyesters of 4-hydroxycyclohexanecarboxylic acid or 4- hydroxybenzoic acid.

Polymers which are also suitable are those predominantly containing ester bonds, but which can also contain other bonds, e.g. polyester amides or polyester imides.

Polyesters containing aromatic dicarboxylic acids have become of the greatest importance, especially the polyalkylene terephthalates. Those novel moulding compounds are therefore preferred, wherein the polyester is composed of at least 30 moi%, preferably of at least 40 mol%, of aromatic dicarboxylic acids, and of at least 30 moM, preferably of at least 40 moi%, of alkylenediols which preferably contain 2 to 12 carbon atoms, based on the polyester.

In this case the alkylenediol is preferably linear and contains 2 to 6 carbon atoms, typically ethylene-, tri-, tetra- or hexamethylene glycol, and the aromatic dicarboxylic acid terephthalic acid andlor isophthalic acid.

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

Polyketones will be understood as meaning plastic materials which are prepared by polymerising carbon monoxide with unsaturated hydrocarbons, such as dislosed, inter alia, in EP-A-0 222 454 or EP-A-0 685 517.

Convenient compositions, as described above, are those wherein components (b) and (c) are present together in an amount of 0.05 to 5 %, preferably of 0.1 to 5 %, typically of 0.1 to 2 %, based on the weight of component (a).

Also preferred are those compositions, wherein the weight ratio of the components (b):(c) is from 10:1 to 1:10, preferably from 5:1 to 1:5, typically from 4:1 to 12.

In addition to the components (b) and (c), the novel compositions can contain additional additives or costabilisers, such as the following:

1. Antioxidants 1.1. Alkylated monophenols, for example 2,6-d i-te rt-b utyl-4- methyl ph en ol, 2-tert-butyi-4,6-dimethylphenol, 2,6-di-tert-butyi-4-ethylphenol, 2,6-di-tert-butyi-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2, 6-dicyclopentyi-4-methylphenol, 2-(a-methylcycl ohexyi)-4,6-dim ethylphenol, 2,6-dioctadecyi-4-methylphenol, 2,4,6-tricyclohexylphenol, 2, 6-di-tert-butyi-4methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyi-4-methylphenol, 2, 4-di methyl-6-(V- methyl undec- V-y1)p henoi, 2,4-dimethyi-6-(1'methyiheptadec-l'-yi)phenol, 2,4-dimethy]-6-(1'-methyltridec-l'-y1)phenol and mixtures thereof.

1.2. A&Ithiomethylphenols, for example 2,4-dioctyithiomethyl-6-tertbutylphenol, 2,4-dioctyithiomethyi-6-methylphenol, 2,4-dioctylthiomethyi6-ethylphenol, 2,6-d i -dodecylth i o m ethyl4-nonylphenol.

1.3. Hydroguinones and alkylated hydroquinones, for example 2,6-di-tertbutyi-4-methoxyphenol, 2,5-di-tert-butyihydroquinone, 2,5-di-te rt-amy] hyd roq u i none, 2,6-diphenyi-4-octadecyloxyphenol, 2,6-di-tertbutyihydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tertbutyl-4-hydroxyanisole, 3,5-di-tert-butyi-4-hydroxyphenyl stearate, bis(3,5-di-tert-buty]-4hydroxyphenyl) adipate.

1.4. Tocopherols, for example a-tocopherol, P-tocopherol, y-tocopherol, 8tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example 2,2'-th iobis (6-te rtbuty]-4-m ethyl phen o 1), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6tert-butyi-3-methylphenol), 4,4'-thiobis(6-tert-butyi2-methylphenol), 4, 4'-thiobis-(3,6-di-sec-amyiphenol), 4,4'-bis(2,6-dimethyi-4hydroxyphenyi)disuifide.

1.6. AlkylidenebisDhenols, for example 2,2'-methylenebis(6-tert-butyi-4methylphenol), 2,2'methylenebis(6-tert-butyi-4-ethylphenol), 2,2'methylenebis[4-methyl-6-(a-methylcyclohexyi)phenol], 2,2'-rn ethyl e nebis(4-methy]-6-cyclohexylphe nol), 2,2'-methylenebis(6-nonyi-4methylphenol), 2,2'-m ethyl e n ebis(4,6-di-tert-b utyl ph e nol), 2,2'ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyi-4isobutylphenol), 2,2'-methylenebis[6-((x-methyibenzyi)-4-nonylphenoll, 2, 2'-methylenebis[6-((x,a-dimethyibenzyi)-4-nonylphenol], 4,4-methy1 enebis(2,6-d i-tert-butyl phenol), 4,4'-methylenebis(6-tert-butyl -2methyl phenol), 1, 1 -bis(5tert-b utyl-4-hyd roxy-2-m ethyl p he nyl) butane, 2,6-b is(3-te rt-b uty]-5-m ethyl -2-hydroxybenzyl) 4methylphenol, 1,1,3-tris(5-tert-butyi-4-hydroxy-2-methylphenyi)butane, 1, 1-bis(5-tert-butyi4-hydroxy-2-methyi-phenyl)-3-n-dodecyimercaptobutane, ethylene glycol bis[3,3-bis(3'-tertbutyi-4'-hydroxyphenyi)butyrate], bis(3-tert-butyi-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3'tert-butyi-2'-hydroxy-5'-methyibenzyi)-6-tert-butyi-4-methylphen yi]terephthalate, 1, 1 -bis-(3,5-dim ethyl -2-hydroxyp he nyl) b utan e, 2,2-bis-(3,5-di-tert-butyi-4-hydroxyphenyl)propane, 2,2-bi s-(5-te rtbutyl-4-hyd roxy2-m ethyl p he nyl)-4-n-dodecyl me rcaptobutane, 1,1,5,5tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. 0-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tertbutyi-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5dimethylbenzyimercaptoacetate, tridecyi-4-hydroxy3,5-di-tertbutylbenzyimercaptoacetate, tris(3,5-di-tert-butyi-4-hydroxybenzyi)amine, bis(4tert-butyi-3-hydroxy-2,6-dimethylbenzyi)dithioterephthalate, bis(3,5di-tert-butyi-4-hydroxybenzyi)suifide, isooctyi-3,5-di-tert-butyi-4hydroxybenzyimercaptoacetate.

1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis-(3,5-ditert-butyi-2-hydroxybenzyi)-malonate, di-octadecyl-2-(3-tert-butyi-4hydroxy-5-methyibenzyi)-malonate, didodecyimercaptoethy]-2,2-bis-(3,5ditert-butyi-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetram ethylb utyi)phe nyl]-2,2-bis(3,5-di -te rt-butyl -4-hyd roxybe n zyl)m alonate.

1.9. Aromatic hydroxybenzyi compounds, for example 1,3,5-tris-(3,5-ditert-butyi-4-hydroxybenzyi)-2,4,6-trimethyibenzene, 1,4-bis(3,5-di-tertbutyi-4-hydroxybenzyi)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tertbutyi-4-hydroxybenzyi)phenol.

1. 10. Triazine Compounds, for example 2,4-bis(octyimercapto)-6-(3,5-ditert-butyi-4-hydroxyanifino)-1,3,5-triazine, 2-octyimercapto-4,6-bis(3,5di-tert-buty]-4-hydroxyanilino)-1,3,5triazine, 2-octyimercapto-4,6-bis(3, 5-di-tert-butyi-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6tris(3,5-di-tertbutyi-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris-(3,5-di-tert-butyi-4hydroxybenzyi) isocyanu rate, 1,3,5-tris(4-tert-butyi-3-hydroxy-2,6dimethyibenzyi)isocyan u rate, 2,4,6-tris(3,5-di-tert-butyi-4hydroxyphenylethyi)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl4hydroxyphenylpropionyi)-hexahydro-1,3,5-tria zine, 1,3,5-tris(3,5dicyclohexyl-4-hydroxybenzyi) isocyan u rate.

1. 11. Benzylphosphonates, for example dimethyi-2,5-di-tert-butyi-4hydroxybenzyiphosphonate, diethyi-3,5-di-tert-butyi-4hydroxybenzyiphosphonate, dioctadecy13,5-di-tert-butyi-4hydroxybenzylphosphonate, dioctadecyl-5-te rt-b utyl-4-hyd roxy-3-m ethyl benzylphosph onate, the calcium salt of the monoethyl ester of 3,5-ditert-butyi-4-hydroxybenzyiphosphonic acid.

1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4hydroxystearanilide, octyl N(3,5-di-te rt-butyl -4-hyd roxyph e n yl) ca rba mate.

1. 13. Esters of B-(3.5-di-tert-buty]-4-hydroxyi2henyi)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,W-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3thiapentadecanol, trim ethylhexanediol, trimethylolpropane, 4-hyd roxym ethyl- 1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1. 14. Esters of Q-(5-tert-bulyi-4-hydroxy-3-methyiphenyi)propionic acid with mono- or polyhydric alcohols, e.g. with 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, tris(hydroxyethyi) isocyanurate, N,W-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3thiapentadecanol, trim ethylhexanediol, trim ethylolpropane, 4hydroxymethyi-l-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1. 15. Esters of 0-(3.5-dicyclohehcy]-4-hydroL(yphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyi)isocyanurate, N,Wbis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trim ethylhexanediol, trimethylolpropane, 4-hydroxymethyl-11 -phospha-2,6,7trioxabicyclo[2.2.2]octane.

1. 16. Esters of 3.5-di-tert-bu!yi-4-hydroxyphenyl acetic acid with monoor polyhydric alcohols, 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(hydroxyethyi)isocyan u rate, N,Wbis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyM -phospha-2,6,7trioxabicyclo[2.2.2]octane.

1. 17. Amides of 0-(3.5-di-tert-buW-4-hydroxyphenyi)propionic acid e.g. N, W-bis(3,5-di-tertbutyi-4-hydroxyphenylpropionyi)hexamethylenediamide, N, N'-bis(3,5-di-tert-buty1-4-hydroxyphenylpropionyi)trimethylenediamide, N, N-bis(3,5-di-tert-butyf-4-hydroxyphenyipropionyi)hydrazide, N,N'-bis[2-(3[3,5-di-tert-buty]-4-hydroxyphenyl]propionyloxy)ethyi]oxamid e (NaugardXL-1 supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C) 1.19. Aminic antioxidants, for example N,N'-di-isopropyi-p- phenylenediamine, N,Wdi-secbutyl-p-phenylenediamine, N,N'-bis(1,4- dimethylpentyi)-p-phenylenediamine, N,W-bis(lethyl-3-methylpentyl)-p- phenylenediamine, N,N'-bis(l-methyiheptyl)-p-phenylenediamine, N,N'dicyclohexyl-p-phenylenediamine, N,N'-diphenyi-p-phenylenediamine, N,N'bis(2-naph- thyl)-p-phenylenediamine, N-isopropyi-N'-phenyi-p-phenylenediamine, N-(1, 3-dimethylbutyi)N'-phenyi-p-phenylenediamine, N -(1 -methyl heptyi)-N'-p he nyi-p-ph enyle n ediam in e, N-cyclohexyi-N'-phenyl-p-phenienediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,W-dimethylN,N'-di-sec-butyf-pphenylenediamine, diphenylamine, N-allyidiphenylamine, 4isopropoxydiphenylamine, N-phenyi-l-naphthylamine, W(4-te rt-octyl p he nyi)- 1 -nap hthylami ne, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tert-octyidiphenylamine, 4-nbutylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4methoxyphenyl)amine, 2,6-di-tert-butyi-4-dimethylaminomethylphenol, 2,4'diaminodiphenyimethane, 4,4'-diaminodiphenyimethane, N, N, N', N'-tetram ethyl -4,4'-diam i nodiphenyl methane, 1, 2-b i s[(2-m ethyl phenyl) am ino]ethan e, 1,2-bis(phenylamino)propane, (o-toiyf)biguanide, b is[4-(V, X-dirn ethyl butyl) p henyl]ami ne, tert-octylated N-phenyi-lnaphthylamine, a mixture of mono- and dialkylated tertbutyl/tertoctyidiphenylamines, a mixture of mono- and dialkylated nonyidiphenylamines, a mixture of mono- and dialkylated dodecyidiphenylamines, a mixture of mono- and dialkylated isopropyi/isohexyidiphenylamines, a mixture of mono- und dialkylated tertbutyidiphenylamines, 2,3A ihydro-3,3-d irn ethyl -4 H- 1 4-be nzothiazin e, phenothiazine, a mixture of mono- und dialkylated tert-butyi/tertoctylphenothiazines, a mixture of mono- und dialkylated tert-octyiphenothiazines, N-allylphenothiazin, N,N,N',N'-tetraphenyi-1,4-diaminobut2-ene, N,N-bis(2,2,6,6-tetramethyi-piperid-4-yi-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate, 2,2,6,6-tetramethylpipeddin4-one, 2,2,6,6-tetram ethyl p i pe ridi n-4-ol.

2. UV absorbers and light stabilisers 2.1. 2-(2'-Hvdroxvohenyl)benzotriazoles, for example 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-(3',5'-ditert-buty]-2'hydroxyphenyi)benzotriazole, 2-(5'-tert-butyi-2'hydroxyphenyi)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3tetramethylbutyi)phenyl)benzotriazole, 2-(X,5'-clitert-butyi-2'hydroxyphenyi)-5-chloro-benzotriazole, 2-(3'-tert-butyi- Z-hydroxy-5'methylphenyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-buty]-2'hydroxyphenyl)benzotriazole, 2(2'-hydroxy-4'-octyloxyphenyi)benzotriazole, 2-(3',5'-di-tert-amyi-2'-hydroxyphenyl)benzotriazole, 2-(3', 5'-bis-((x, ot-di methyl benzyi)-2'-hydroxyphenyi)benzotriazole, 2-(3'-tert-buty)-2'hydroxy-5'-(2-octyloxycarbonylethyi)phenyi)5-chloro-ben zotriazole, 2-(3'tert-butyi-5'-[2-(2ethyl hexyloxy)-carbonyl ethyl] -2'-hydroxyphenyl)-5ch loro-be nzotriazole, 2-(3'-tert-buty]-2'-hydroxy-5'-(2methoxycarbonylethyi)phenyl)-5-chloro-benz otriazole, 2-(3'-tert-butyi-2'hydroxyT-(2-m eth oxyca rbo nyl ethyl) phenyl)be nzotriazole, 2-(3'-tertbutyl-2'-hydroxy-5'-(2-octyloxy- carbonyl ethyl) phenyl) be nzotriazol e, 2-(3'-tert-butyl-S'-[2-(2ethyihexyloxy)carbonylethyll-2'hydroxyphenyi)benzotriazole, 2-(3'-dodecyi2'-hydroxy-5'-methylphenyi)benzotriazole, 2-(Xtert-butyi-2'-hydroxy-5'-(2isooctyloxycarbonylethyl)phenyibenzotriazo le, 2,2'-methylene-bis[4-(1,1, 3,3-tetram ethy[butyl)-6-b enzotriazole-2-yl phenol]; the transesterification product of 2[3'-tert-butyi-5'-(2methoxycarbonylethyi)-2'-hydroxyphenyll-2H-benzotria zole with polyethylene glycol 300; [R-CH,CHi-COOCH2CH2+ where R = 3'-tert-butyi-4'-hydroxy5'-2H2 benzotriazol-2-yl phenyl, 2-[2'-hydroxy-3'-(cc,cc-dimethyibenzyl)-5'-(1,1, 3,3-tetramethyibutyl)phenyl]benzotriazole; 2 - [2-h yd roxy-X-(1, 1, 3,3 - tetram ethyl b u tyl) -5, -(cc, a-d im ethylbenZY1)phenyQbenzotriazole.

2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4octyloxy, 4-decyloxy, 4-dodecyioxy, 4-benzyloxy, 4,2',4-trihydroxy and Xhydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, as for example 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyi) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-buty]-4- hydroxybenzoate, hexadecyl 3,54-te rt-butyl-4- hyd roxybe n zo ate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyi-4,6-di-tert- butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl cc-cyano-o,p-diphenylacrylate, isooctyl a-cyano-p,p-diphenylacrylate, methyl (x-carbomethoxyci n na mate, methyl a-cyano-p-methyi-p-methoxy-cinnamate, butyl (x-cyano-p-methyl-p-methoxycinnamate, methyl (x-carbomethoxy-p-methoxycinnamate and N-(pcarbomethoxy-p-cyanovinyi)-2-methylindoline.

2.5. Nickel compounds, for example nickel complexes of 2,2'-th io-b is-[4(1,1,3,3-te tram ethylbutyi)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or Ncyclohexyidiethanolamine, nickel dibutyidithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-ditertbutylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2hyd roxy-4-m ethyl ph enyl undecyiketoxime, nickel complexes of 1-phenyi4-lauroyi-5-hydroxypyrazole, with or without additional ligands.

2.6. Sterically hindered amines, for example b is (2,2,6,6-tetram ethyl 4-pi pe ridyl)se bacate, bis(2,2,6,6-tetramethyi-4-piperidyi)succinate, bis(1,2,2,6,6-pentamethyi-4-piperidyf)sebacate, bis(l-octyloxy-2,2,6,6tetramethy]-4-pipeddyi)sebacate, bis(1,2,2,6,6-pentamethyi-4-piperidyl) nbutyi-3,5-di-tert-butyl-4-hydroxybenzyimalonate, the condensate of 1-(2hydroxyethyi)-2,2,6,6-tetramethyi-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N, W-bi s (2,2,6,6-tetram ethyl -4-p ipe ridyl) h examethyle n ediam i ne and 4-tert-octylamino-2,6-dichloro-1,3,5triazine, tris (2,2,6,6-tetram ethyl -4-pi p e ridyl) nitri 1 otriacetate, tetrakis(2,2,6,6-tetram ethyl -4-pi pe ri dyi) - 1,2,3,4-butane-tetraca rboxyl ate, 1,1'-(1,2-ethanediyi)-bis(3,3,5,5-tetram ethyl piperazi none), 4-benzoy]-2,2,6,6-tetramethylpiperidine, 4-stearyloxy2,2,6,6tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyi-2-(2hydroxy-3,5di-tert-butyibenzyi)malonate, 3-n-octy]-7,7,9,9-tetram ethyl1, 3,8-triazaspi ro[4.5]decan-2,4dione, bis(l-octyloxy-2,2,6,6tetramethylpiperidyi)sebacate, bis(l-octyloxy-2,2,6,6tetramethylpiperidyi)succinate, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethy]-4-piperidyi)hexamethylenediamine and 4-morphoiino-2, 6-dichloro-1,3,5-triazine, the condensate of 2-ch 1 o ro-4,6-b is (4-nbutylam in o-2,2,6,6-tetram ethyl pipe ri dyl)-1,3,5-triazine and 1,2bis(3aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-nbutylamino-1,2,2,6,6-pentam ethyl pi peridyl)- 1, 3,5-tri azi n e and 1,2bis-(3-aminopropylamino)ethane, 8-acetyl-3-dodecyi-7,7,9,9-tetramethyi-1, 3,8-triazaspiro[4.5]decane-2,4-di one, 3-dodecyi-l-(2,2,6,6-tetramethyi-4piperidyl)pyrrolidin-2,5-dione, 3-dodecyi-l-(1,2,2,6,6-pentamethyi-4piperidyi)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4stearyloxy-2,2,6,6-tetram ethyl pipe rid in e, a condensation product of N, N'-bis(2,2,6,6-tetram ethyl-4-piperidyi) h exam ethyl enediam i ne and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetram ethyl pipe ridine (CAS Reg. No. [136504-96-6]); N-(2,2,6,6-tetramethyi-4-piperidyl)-n-dodecyisuccinimid, N-(1,2,2,6,6-pentamethyi-4-pipe ridyi)-n-dodecyisucci n i mid, 2-undecy]7, 7,9, g-tetram ethyl- 1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9tetram ethyl -2-cycloun decyl - 1 -oxa-3,8-di aza-4oxospi ro [4,5]decane und epichlorohydrin, 1,11-b is(l, 2,2,6,6-p e ntam ethyl -4-pi pe ridyl oxyca rbonyl)-2-(4-m ethoxyph e nyi) ethe n e, N,Kbisformyl-N,N'-bis(2,2,6,6-tetramethyi-4-piperidyi)hexamethylenediamin e, diester of 4-methoxymethylene-malonic acid with 1,2,2,6,6-pentamethyi-4hydroxypiperidine, poly[m ethyl p ropyl 3-oxy-4-(2,2,6,6-tetramethyl-4piperidyl)]siloxane, reaction product of maleic acid anhydridea-olefincopolymer with 2,2,6,6 -tetram eth yi-4-am i nop ipe rid i ne or 1,2,2,6, 6-pentamethyl-4aminopiperidine.

2.7. Oxamides, for example 4,4-dioctyloxyoxanilide, 2,2'diethoxyoxanilide, 2,2'-dioctyloxy5,5'-di-tert-butoxanilide, 2,2'didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'bis(3-dimethylaminopropyi)oxamide, 2-ethoxy-5-tert-butyi-2'-ethoxanifide and its mixture with 2-ethoxy-2'-ethyi-5,4'-di-tert-butoxanifide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxvphenyi)-1.3.5-thazines, for example 2,4,6-tris(2-hydroxy4-octyloxyphenyi)11,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyi)-4,6bis(2,4-dimethylphenyi)-1,3,5-triazine, 2(2,4-d i hyd roxyph e nyl) -4,6bis (2,44 methyl p he nyi)- 1, 3,5-triazi n e, 2,4-bis(2-hydroxy-4propyloxyphenyi)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4octyloxyphenyi)-4,6-bis(4-methylphenyi)-1,3,5-triazine, 2-(2-hydroxy-4dodecyloxyphenyi)-4,6-bis(2,4-dimethylphenyi)-1,3,5-triazine, 2-(2-hyd roxy-4-tridecyloxyph e nyl)-4,6-bis (2,4A i methyl p henyi)- 1 3,5-tri azine, 2- [2-hyd roxy-4-(2-hydroxy-3-butyloxy-propoxy) ph e nyll-4,6-bis (2,44m ethyl) - 1,3,5-td azine, 2-[2 -hyd roxy-4- (2-hyd roxy-3-octyloxyp ropyloxy) p h enyll-4,6-b is(2,4-d i m ethyl) - 1,3,5 triazine, 2-[4(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyi)-4,6-bis(2,4dimethyl phenyl)- 1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl1-4,6bis (2,4A i methyl phe nyi)- 1, 3,5-triazi ne, 2-(2hydroxy-4-hexyloxy)phenyi-4,6-diphenyi-1,3,5triazine, 2-(2-hydroxy-4methoxyphenyi)-4,6-diphenyi-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4(3butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyi)-4-(4methoxyphenyi)-6-phenyi-1,3,5-thazine, 2-{2-hydroxy-4-[3-(2-ethyihexy]-1oxy)-2-hydroxypropyloxy]phenyi)-4,6-bis(2,4-dimethylphenyi)-1,3,5triazine.

3. Metal deactivators, for example N,N'-diphenyloxamide, N-salicylai-N'salicyloyl hydrazine, N,Wbis(salicyloyl) hydrazine, N,N'-bis(3,5-di-tertbutyi-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloy lam ino- 1,2,4triazole, bis(benzyiidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyihydrazide, N,Wcliacetyladipoyl dihydrazide, N,Wbis(salicy]oyl)oxalyl dihydrazide, N,N'-bis(salicyloyi)thiopropionyl dihydrazide.

4. Phosphites and Phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosp h ite, cl istearyl pentae ryth ritol di phosphite, tris(2,4-di-tert-butyl phenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritoi diphosphite, bis(2,6di-tert-butyi-4-methylphenyi)pentaerythritol diphosphite, diisodecyloxypentaerythritol di- phosphite, bis(2,4-di-te rt-butyl-6-m ethyl p henyi) pentaeryth rito 1 diphosphite, bis(2,4,6-tris(tertbutylphenyl)pentaerythritol diphosphite, tristeary] sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'- biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyi-12Hdibenz[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12methyi-dibenz[d,g]1,3,2-dioxaphosphocin, bis (2,4-d i-te rt-b utyl-6 methyl phenyl) methyl phosphite, bis(2,4-ditert-butyl-6-methylphenyi) ethyl phosphite, 2,2',2"-nitrilo[triethyltris(3,3',5,5'-tetra-tert-butyi1, 1'-bipheny]-2,2'-diyi)phosphite], 2-ethylhexyi(3,3',5,5'-tetra-tert-butyl1,1'-biphenyl-2,2'-diy1)phosphite.

5. Hydroxylamines, for example, N,N-dibenzyihydroxylamine, N, N-d i ethyl hyd roxylami ne, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,Nditetradecylhydroxylarnine, N,Ndihexadecylhydroxylamine, N,Ndioctadecylhydroxylarnine, Whexadecyl-N-octadecylhydroxylamine, Nheptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

6. Nitrones, for example, N-benzyi-alpha-phenyl-nitrone, N-ethyi-alphamethyi-nitrone, N-octyi-alpha-heptyl-nitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyi-alpha-tridcyi-nitrone, Nhexadecyi-alpha-pentadecylnitrone, N-octadecyi-alpha-heptadecyi-nitrone, Whexadecylalpha-heptadecylnitrone, N-ocatadecyi-alpha-pentadecyi-nitrone, Wheptadecyl-alphaheptadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example, dilauryl thiodipropionate or disteary] thiodipropionate.

8. Peroxide scavengers, for example esters of P-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazoie, zinc dibutyidithiocarbamate, diactadecyl disulfide, pentaerythritol tetrakis(pdodecyimercapto)propionate.

9. Polyamide stabilisers, for example, copper salts in combination with iodides andlor phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilisers, for example, melamine, polyvinyl pyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zink pyrocatecholate.

11. Nucleating agents, for example, inorganic substances such as talcum, 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 and the salts thereof, e. g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers).

12. Fillers and reinforcing nents, for example, calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.

13. Other additives, for example, plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed in 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-431661 1; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2- acetoxyethoxy)phenyi]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert- butyl-3-[4-(2-stearoyioxyethoxy)phenyllbenzofuran-2-one, 3j-b is[5,7-d i- te rt-butyl -3- (4-[2- hyd roxyeth oxy] p hen yi) ben zof u ran -2one], 5, 7-di-tert-butyi-3-(4-ethoxyphenyi)benzofuran-2-one, 3-(4-acetoxy-3,5-di methyl ph enyl)-5,7-di-tert-butyi-benzofuran-2-one, 3-(3,5-dimethyi-4- pivaloyloxyphenyi)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,4- dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(2,3-dimethyl ph e nyl)-5,7-di -te rt-butyl -ben zof u ran -2-on e.

With the exception of the benzofuranones listed under item 14, the costabilisers are added typically in concentrations of 0.01 to 10 %, based on the total weight of the stabilising polyamide, polyester or polyketone.

Further preferred compositions comprise, besides the components (a), (b) and (c), further additives, preferably antioxidants, light stabilisers andlor processing stabilisers.

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

Further additional additives (stabilisers) which are also particularly preferred are benzofuran-2-ones, such as those disclosed, inter alia, in US-A-4 325 863, US-A-4 338 244, US-A-5 175 312, US-A-5 216 052, US-A-5 252 643, DE-A-4 316 611, DE-A-4 316 622, DE-A-4 316 876, EP-A-0 589 839 and EP-A-0 591 102.

Illustrative examples of such benzofuran-2-ones are compounds of formula W15 R'14 0 1 r_ c =0 R'143 1 \\ R1 1 W1 2 H wherein R', i is an unsubstituted or substituted carbocyclic or heterocyclic aromatic ring system; R12 is hydrogen; R'14 is hydrogen, alkyl of 1 to 12 carbon atoms, cyclopenty], cyclohexy], or chloro; 0 11 R13 has the meaning of R12 or R,,, or is a radical of formula -(CH.)- C-OR' S 0 0 0 11 11 11 -(CH -C-O-A-0-C-(CH -E -'-"4kMl7)2 2)s 2)s -(CH2)s 0 0 0 0 11 11 11 11 18 5 5 -1'4h--A-0-C-(CH-E -C-NR'-A-NR' C-(CH E, -(CH k' ia - (CH2)s 18 2) 2) 2)s 0 0 0 11 /-\ 11 11 CH)-E -CH2-S-R'ig, -CH(C,H -C-OR',, or-D-E, -C-N N-C-( 25 5) -(CH2)s wherein R16 is hydrogen, alkyl of 1 to 18 carbon atoms, alkyl of 2 to 18 carbon atoms which is interrupted by oxygen or sulfur, dialkylaminoalkyl having a total of 3 to 16 carbon atoms, cyclopentyl, cyclohexyl, phenyl, or phenyl which is substituted by 1 to 3 alkyl radicals having a total of at most 18 carbon atoms; s is 0, 1 or 2; substituents R17 are each independently of one another hydrogen, alkyl of 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl which is substituted by 1 or 2 alkyl radicals having a total of at most 16 carbon atoms, a radical of formula -C2H40H, -C2H4-0-CtH2t.,, or 0 11 - C2lij- 0 C - R'20, or, together with the linking nitrogen atom, form a piperidine or morpholine radical; t is 1 to 18; R2o 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; R18 is hydrogen, alkyl of 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl; phenyl which is substituted by 1 or 2 alkyl radicals having a total of at most 16 carbon atoms, or benzyi; - R'19 is alkyl of 1 to 18 carbon atoms; D is -0-, -S-, -SO-, -S02- or - C(R'21)2- substituents R'21 are each independently of the other hydrogen or Cl- C16alkyl, the two R21 together containing 1 to 16 carbon atoms, or W21 is phenyl or a radical of formula 0 0 11 11 -C-OR',, or -(CH -C-IM(R'17)2, wherein s, W16 and R'17 are as defined (CH2)s 2)s above; E is a radical of formula F15 R'14 0 c j R'i 1 R 12 H wherein R', 1, R'12and W14are as defined above; and R'15 is hydrogen, alkyl of 1 to 20 carbon atoms, cyciopentyl, cyclohexyl, chloro, or a radical 0 0 11 11 of formula l, v, -CHi--C-N(R'17)2, wherein W16and W17are as de fined above, or W15, together with W14, forms a tetramethylene radical.

Preferred benzofuran-2-ones are those, wherein R' 13is hydrogen, alkyl of 1 to 12 carbon 0 11 atoms, cyclopentyl, cyclohexyl, chloroora radical of formula -(CH 2); -C-OR'le, 0 11 or -D-E, wherein s, W%, R'17, D and E are as defined above, R16 is -C-N(R'17)2 (CH 2)s preferably hydrogen, alkyi of 1 to 18 carbon atoms, cyclopentyl or cyclohexyl.

Preferred benzofuran-2-ones are also those, wherein R',, is phenyl or phenyl which is sub- stituted by 1 or 2 alkyl radicals having a total of at most 12 carbon atoms; R' 12 is hydrogen; R'14is hydrogen or alkyl of 1 to 12 carbon atoms; 0 11 -C-OR '16 R'13 is hydrogen, alkyl of 1 to 12 carbon atoms, -(CH 2)s 0 11 -N(R '17)2 or -D-E; W15 is hydrogen, alkyl of 1 to 20 carbon atoms, -C (CH 2)s 0 0 11 11 -CHi--u-uml, or -CHi--C-N(R'17)2, or R'15, together with R' 14, forms a tetramethylene radical, wherein s, R'16, R' 17, D and E are as defined at the outset.

Particularly interesting benzofuran-2-ones are also those, wherein W13 is hydrogen, alkyl containing 1 to 12 carbon atoms or -D-E; W12 and W14 are each independently of the other hydrogen or alkyl of 1 to 4 carbon atoms; and W15 is alkyl of 1 to 20 carbon atoms, wherein D and E are as defined at the outset.

Of particular interest are also those benzofuran-2-ones, wherein W13 is alkyl of 1 to 4 carbon atoms or -D-E; W12 and R14 are hydrogen; and W15 is alkyl of 1 to 4 carbon atoms, cyclopentyl or cyclohexyl, D is a - C(R21)2group and E is a radical of formula WIS R'14 0 0 c 1 R11 W12, H the substituents W21 being identical or different from each other and are each alkyl of 1 to 4 carbon atoms, and W,,, F12, R14 and R'15 are as defined above.

The amount of benzofuran-2-ones additionally employed can vary within wide limits. They can be present in the novel compositions typically in amounts of 0.0001 to 5 by weight, preferably of 0.001 to 2 by weight, most preferably of 0.01 to 2 % by weight.

The components (b) and (c) and any further additives are incorporated into component (a) [polyamide, polyester or potyketone] by known methods, typically before or during shaping, or alternatively by applying the dissolved or dispersed components (a) and (b) to the component (a), with subsequent evaporation of the solvent, when used. The components (b) and (c) can also be added to the materials to be stabilised [component (a)] in the form of a masterbatch which contains these components in a concentration of 2.5 to 25 % by weight.

The components (b) and (c) can also be added before or during polymerisation or before crosslinking.

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

Components (b) and (c) can also be sprayed onto the component (a) to be stabilised. They are able to dilute other additives (e.g. the standard additives cited above) or their melts, so that that they can also be sprayed onto the component (a) to be stabilised together with these additives. Application by spraying during deactivation of the polymerisation catalysts is particularly advantageous, in which case the steam used for the deactivation may be used for spraying.

The polyamides, polyesters and polyketones stabilised in this manner can be used a wide range of forms, typically including films, fibres, filaments, moulded articles, profiles or binders for paints, adhesives or putties.

The components (b) and (c) are particularly suitable as processing stabilisers (heat stabilisers). To this end they are preferably added to component (a) before or during processing.

A preferred embodiment of this invention is therefore the use of the phosphite of formula 1 and at least one compound of formula 11 as stabilisers, preferably as processing stabilisers (heat stabilisers), for polyamides, polyesters or polyketones against oxidative, thermal or lightinduced degradation.

The components (b) and (c) are distinguished by their advantageous colour behaviour, i.e. minor discoloration of the polyamides, polyesters and polyketones during processing.

This invention also relates to a process for stabilising a polyamide, polyester or polyketone against oxidative, thermal and/or light-induced degradation, which comprises incorporating therein, or applying thereto, the phosphite of formula 1 and at least one compound of formula 11.

This invention also relates to a stabiliser mixture comprising (i) the phosphite of formula 1 and (5) at least one compound of formula H.

Preferred stabiliser mixtures are also those, wherein the weight ratio of components (i):(ii) is from 10:1 to 1:10, preferably from 5:1 to 1:5, typically from 4:1 to 12.

The preferred compounds of formula 11 for use as stabilisers, the process for stabilising, and the stabiliser mixture are the same as those described for the compositions with a polyamide, polyester or polyketone.

The stabiliser mixtures of components (i) and (ii) are called LC blends (low color blends). They are distinguished by excellent storage stability, low volatility and superb free flowing properties. The LC blends cited in Table 1 are particularly preferred.

Table 1:

LC Blend Component (i) Component (ii) Weight ratio (i) (ii) A Irgafos12a) Irganox1 01 ob) 1 A B I rgafos1 2) Irganox1 01 ob) 2: 1 c Irgafos"12a) Irganox1 01 ob) 1 2 D Irgafos12 a) Irganox1 01 ob) 4 1 E 1 rgafos"1 2 a) irganox'3114c) 1 1 F 1 rgafos1 2a) Irganoxl 098d) 1 1 G 1 rgafos1 2a) Irganox"1 098 d) 1 2 H Irgafos"12a) irganox"1 076e) 4 1 Irgafos12a) irganox"1 076e) 2 1 a) Irgafos12 conforms to the compound of formula 1. b) Irganox1010 conforms to the compound of formula I lc. c) irganox"3114 conforms to the compound of formula lig. d) Irganox&1 098 conforms to the compound of formula 1 la. e) Irganox1 076 conforms to the compound of formula lib.

30- The invention is further illustrated by the following Examples in which parts and percentages are by weight.

Example 1: Stabilisation of polyamide 6.

parts of unstabilised polyamide 6 granulate (Ultrarnide133, supplied by BASIF) are powdered by cryogenic grinding and the stabilisers of Table 2 are added. The mixture is mixed with a Henschel mixer for 2 minutes. The powder so obtained is dried at 801C for 6 hours, extruded in an extruder (type Berstorff) at a maximum of 2400C and then granulated. The granulate so obtained is moulded on an injection moulding machine at a maximum of 2400C to dumbbells 1.0 mm thick and to plates 2.0 mm thick.

The dumbbells are aged in a circulating air oven at 1400C. The continuation of the ageing is observed at intervals of 1-3 days by determining the force-elongation diagrams. The end point is defined as the time after which the residual strain has fallen to 50 % of its starting value. The greater the time, the better the stabilisation. The results are summarised in Table 2.

The plates are aged in a circulating air oven at 801C over 1500 hours. The yellowness index (Y1) of these plates is determined in accordance with ASTM D 1925-70. Low Y1 values denote minor discoloration, high Y1 values denote strong discoloration of the samples. The less discoloration, the more effective the stabiliser mixture. The results are summarised in Table 2.

Table 2:

Time in hours to 50 % Yellowness Index Example Stabiliser after 1500 hours residual strain at 140C at 801C (dumbbells) (plates) 1 a 12 51.5 0.2 % Irgafos168 a) 1 b 282 50.0 0.2 % frganoxal 098 b) 0.2 % 1 rgafosl 2c5 1 c 369 42.0 0.2 % 1 rganox1 098 b) a) Irgafos'l 68 (Ciba-Geigy) is tris(2,4-di-tert-butylphenyi)phosphite.

b) Irganoxe1098 (Ciba-Geigy) is N,N'-bis(3,5-di-tert-butyi-4hydroxyphenylpropionyi)hexa- methyl en ediami ne (compound of formula fla).

H3C \ c,CH3 H3C 0 HO CHi--CHi-- C-NI-1-(CH2)3 (11a) H3C ---- c H3C / CH3 -2 c) Irgafos"12 (Ciba-Geigy) is 2,2',2"-nitrilo[triethyi-tris(3,3'5,5-tetra- tert-butyi-1,1'-biphenyl2,2'-diyl)phosphite]; Chemical Abstract "Registry" number: 80410-33-9 and is the compound of formula 1.

(CHIC C(CHI 0 P-O-CH2CHi----N 0 (CHIC C(CH The results of Table 2 show that the novel stabiliser mixture (Example 1 c) is markedly more effective than the known stabiliser mixture (Example 1 b).

Claims (20)

What is claimed is

1. A composition, comprising a) a polyamide, polyester or polyketone which is subject to oxidative, thermal or lightinduced degradation, b) the phosphite of formula 1 (CHIC C(CHI 0 P-O-CH2CHI----N 0 (CHIC C(CHI 3 and c) at least one compound of formula 11 H3C \ c ',CH3 H3C.1 HO X-R2 L R1 n wherein R, is Cl-C4alkyl, n is 1, 2, 3 or 4, 0 0 Xismethylene, -CHi-Crl2 C-v- or -CH2 k,-u-CHi--CHj-- Y is oxygen or -NH-; and, if n = 1, 0 X is -CH2 CHI-C-Y- wherein Y is bound to R2, and R2 is Cl-C2salky]; and, if n = 2, 0 X is -CH2 CH2 C-v wherein Y is bound to R2, and R2 is C2-C12alkylene, C4-C12alkylene which is interrupted by oxygen or sulfur; or, if Y is -NH-, R2 is additionally a direct bond; and, if n = 3, 0 X is methylene ot -CH2 C-O-CHI-CH2 wherein the ethylene group is bound to R2, and 1 R2 is Y. Y and, N Y N 0 if n = 4, 0 Xis -CH2 CHi-C-T- wherein Yisboundto R2, and R2 is C4-Cloalkanetetrayl.

2. A composition according to claim 1, wherein component (c) is at least one compound of formula 11, wherein, if n = 1, R2 is Cl-C20alkyl.

3. A composition according to claim 1, wherein component (c) is at least one compound of formula 11, wherein, if n = 2, R2 is C2-Caalkylene, C4-C8alkylene which is interrupted by oxygen or sulfur; or, if Y is -NH-, R2 is additionally a direct bond; and, if n = 4, R2 is C4-C8alkanetetray].

4. A composition according to claim 1, wherein component (c) is at least one compound of formula 11, wherein R, is methyl or tert-butyl, n is 1, 2 or 4, 0 xis Y is oxygen or -NH- and, if n = 1, R2 is C14-Claalkyl; and, if n = 2, R2 is C,-Cralkylene, or C4-C6alkylene which is interrupted by oxygen; and, if n = 4, R2 is C4-C6alkanetetrayl.

5. A composition according to claim 1, wherein component (c) is at least one compound of formula lia, lib, lic or lid H3C \ CH H3C 0 HO CHI-CH2 C-NI-1-(C1-12k (11a) H3c-, c H3C / CH3 2 H3C \,CH3 H3C 0 11 HO CHi--CHI--C-O-C,,,H37 H3C --- c H3C / CH 3 H 3C \ ', CH3 H3C 0 11 HO CHi--CHi--C-O-CH--C H3 c / c, CH3 H 3C -4 37 H3C CH3 ---3 H3 H CH2 CH2- G0- CHj- CH2 0 CHi H3 L J 2

6. A composition according to claim 5, wherein component (c) is a compound of formula lla, fib or 0

7. A composition according to any preceding claim, wherein the polyamide is a polyamide 6, 0 polyamide 6.6, polyamide 11 or polyamide 12, or a copolymer thereof.

8. A composition according to any one fo claims 1 to 6, wherein the polyester is a PET, PEW or 0 PBT, or a copolymer thereof.

9. A composition according to any preceding claim, wherein components (b) and (c) are present together in an amount of 0.05 to 5%, based on the weight of component (a).

10. A composition according to any preceding claim, wherein the weigt ratio of components (bO:(c) is from 10: 1 to 1: 10.

11. A composition according to any preceding claim, additionally comprising further additives 1 besides the components (b) and (c).

38

12. A composition according to claim 11, comprising as additional additives phenolic anti-oxidants, light stabilisers andlor processing stabilisers.

13. A composition according to claim 11, comprising as additional additive at least one compound of the benzofuran-2-one type.

14. Use of the phosphite of formula I and at least one compound of formula 11 as defined in any one of claims 1 to 6 as stabilisers for polyamides, polyesters or polyketones against oxidative, thermal andlor light-induced degradation.

15. Use according to claim 14 as processing stabilisers.

16. A process for stabilising a polyamide, polyester or polyketone against oxidative, thermal andlor 0 light-induced degradation, which comprises incorporating therein, or applying thereto, the phosphite of formula 1 and at least one compound of formula 11 as defined in any one of claims 1 to 6.

17. A stabiliser mixture comprising (i) the phosphite of formula 1 and (ii) at least one compound of 0 formula H as defined in any of claims 1 to 6.

18. A stabiliser mixture accordin. to claim 17, wherein the weight ratio of the components (i):(ii) is from 10: 1 to 1: 10.

39

19. A stabiliser mixture according to claim 17 substantially as hereinbefore described.

0

20. A composition according to claim 2 substantially as hereinbefore described with reference to the foregoing Examples.