JPH1036661A - Stabilization of polyamide, polyester and polyketone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stabilize a polyamide, a polyester or a polyketone against degradation induced by oxidation, heat or light by using a composition prepared by adding a specified phosphite and a sterically hindered phenol to the polymer. SOLUTION: This composition comprises a polyamide, a polyester or a polyketone liable to degradation induced by oxidation, heat or light, a phosphite represented by formula I, and a compound represented by formula II (R1 is a 1-4C alkyl; n is an integer of 1-4; X is methylene or a group represented by formula III; Y is O or -NH-; when n=1, X is bonded to a group V, and Y is bonded to R2 (e.g. 2-12C alkylene); when n=3, X is bonded to methylene or a group of formula VI (the ethylene group is bonded to R2 (formula III)); and when n=4, X is bonded to a group represented by formula VIII, and Y is bonded to R2 (4-10C alkanetetrayl)).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a composition comprising a polyamide, polyester or polyketone, a specific organic phosphite (Irgafos 12, from Ciba-Geigy) and a sterically hindered phenol, oxidative, thermal and / or phenolic. Or to their use for stabilizing polyamides, polyesters or polyketones against light-induced disintegration, and to a method for stabilizing these plastic materials.

[0002]

From U.S. Pat. No. 4,360,617, a mixture of stabilizers containing symmetric triarylphosphites and certain antioxidants is known to be capable of protecting organic materials against oxidative, thermal or light-induced degradation. It is known that it is particularly suitable for protecting polyurethane, polyacrylonitrile, polyamide 12 or polystyrene. Tris (2,4-di-tert-butylphenyl) phosphite (registered trademark Irgafos 168 manufactured by Ciba-Geigy)
Are disclosed as preferred triaryl phosphites.

[0003] In polyamides, polyesters and polyketones, these known stabilizer mixtures have not fulfilled all of their requirements. It is known that the mixture of stabilizers reduces the starting color and color development of the polyamide during oven aging and that they reduce the mechanical properties of the polyamide during oven aging and light exposure. Have been. A disadvantage of these stabilizer mixtures is that often their phosphites tend to bloom.

[0004] US Patent Nos. 4,318,845 and 4,374,219 disclose cyclic 1,1'-biphenyl-.
2,2'-diylphosphite and alkylidyne-
Alkanolamine esters of 1,1'-biphenyl-2,2'-diylphosphite are disclosed as stabilizers for organic polymers and lubricating oils, especially as processing stabilizers for polyolefins, elastomers, polyesters and polycarbonates. I have.

[0005]

SUMMARY OF THE INVENTION US Patent Specification No. 43
Stabilizer mixtures containing very specific sterically hindered phenols together with very specific phosphites selected from 18845 and 4374219 are now found to be particularly suitable as stabilizers for polyamides, polyesters or polyketones. Was found. The polyamides, polyesters or polyketones so stabilized have improved properties against oxidative, thermal and / or light-induced degradation and the new phosphites do not bloom.

[0006]

SUMMARY OF THE INVENTION Accordingly, the present invention is directed to a) a polyamide, polyester or polyketone which is susceptible to oxidative, thermal or light induced degradation.

Embedded image And c) at least one of the following formulas II:

Embedded image (Wherein, R ₁ represents an alkyl group having 1 to 4 carbon atoms, n represents 1, 2, 3 or 4; X represents a methylene group;

Embedded image Y represents an oxygen atom or —NH—, and when n = 1, X represents the following formula:

Embedded image The stands, Y is bonded to R _2, and R ₂ represents an alkyl group having 1 -C 25 atoms, and for n = 2 X the following formula

Embedded image The stands, Y is bonded to R _2, and R ₂ is either an alkylene group of alkylene 2 to 12 carbon atoms, C 4 -C interrupted by an oxygen atom or a sulfur atom 12, or When Y represents -NH-, R
₂ further represents a direct bond, and when n = 3, X is a methylene group or

Embedded image The represents an ethylene group in the formula is bonded to R _2, and R ₂ is the formula

Embedded image And when n = 4, X is

Embedded image The stands, Y is bonded to R _2, and R ₂ represents a alkanetetrayl group 10 from 4 carbon atoms. )).

[0007]

Detailed Description of the Invention Alkyl groups having up to 25 carbon atoms are branched or linear groups, typically methyl, ethyl, propyl, isopropyl, n
-Butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-ethylbutyl group, n-pentyl group, isopentyl group, 1-methylpentyl group, 1,3-dimethylbutyl group, n-hexyl group , 1-methylhexyl group, n-
Heptyl group, isoheptyl group, 1,1,3,3-tetramethylbutyl group, 1-methylheptyl group, 3-methylheptyl group, n-octyl group, 2-ethylhexyl group,
1,1,3-trimethylhexyl group, 1,1,3,3-
Tetramethylphenyl group, nonyl group, decyl group, undecyl group, 1-methylundecyl group, dodecyl group, 1,
1,3,3,5,5-hexamethylhexyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, eicosyl group, or docosyl group. Preferred meanings of R ₁ are methyl and tert-butyl. R ₂ particularly preferably represents an alkyl group having 1 to 20 carbon atoms, especially an alkyl group having 1 to 18 carbon atoms, typically an alkyl group having 4 to 18 carbon atoms. R ₂ particularly preferably represents an alkyl group having 8 to 18 carbon atoms, in particular an alkyl group having 14 to 18 carbon atoms, typically an alkyl group having 18 carbon atoms.

The alkylene group having 2 to 12 carbon atoms is a branched or linear group, and is typically an ethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group. , A decamethylene group or a dodecamethylene group. R ₂ particularly preferably represents, for example, an alkylene group having 2 to 10 carbon atoms, especially an alkylene group having 2 to 8 carbon atoms. R ₂ particularly preferably represents, for example, a C 4 -C 8 alkylene group, in particular a C 4 -C 6 alkylene group, typically a hexamethylene group.

C 4 -C 12 alkylene groups interrupted by oxygen or sulfur atoms are interrupted once or several times and are typically —CH ₂ —
_{O-CH 2 CH 2 -O-} CH 2, -CH 2 - (O-CH
_{2 CH 2) 2 O-CH} 2 -, - CH 2 - (O-CH 2 C
_{H 2) 3 O-CH 2} -, - CH 2 - (O-CH 2 CH
_{2) 4 O-CH 2 -} , - CH 2 CH 2 -O-CH 2 CH
_{2 -O-CH 2 CH 2 -} , or -CH ₂ CH ₂ -S
-CH ₂ CH ₂ - represents a. R ₂ is particularly preferably, for example, a C 4 -C 10 alkylene group interrupted by an oxygen or sulfur atom, especially a C 4 -C 8 alkylene group interrupted by an oxygen or sulfur atom, typically Represents an alkylene group having 4 to 6 carbon atoms interrupted by an oxygen atom or a sulfur atom.
R ₂ is particularly preferably —CH ₂ CH ₂ —O—CH ₂ CH
₂ -O-CH ₂ CH ₂ - or -CH ₂ CH ₂ -S-
Represents CH ₂ CH ₂ —.

C 4 -C 10 alkanetetrayl groups typically have the formula

Embedded image It is represented by Pentaerythritol is preferred.

Component (c) is also a mixture of different sterically hindered phenols of the formula II. Compounds of interest include, as component (c), at least one compound of the formula II wherein, where n = 1, R ₂ has 1 to 2 carbon atoms.
Represents an alkyl group of 0. ).

Preferred compositions are those in which component (c) is at least one compound of formula II wherein n is 2, R ₂ is an alkylene group having 2 to 8 carbon atoms, an oxygen atom or a sulfur atom. Represents an interrupted C 4 -C 8 alkylene group, or Y represents —NH—,
R ₂ further represents a direct bond, and when n = 4, R ₂ represents an alkanetetrayl group having 4 to 8 carbon atoms. )
Is a composition.

Preferred compositions are those wherein component (c) is at least one compound of formula II wherein R ₁ is methyl or tert-butyl, n is 1, 2 or 4; Is

Embedded image Y represents an oxygen atom or -NH-, and when n = 1, R ₂ represents an alkyl group having 14 to 18 carbon atoms, and when n = 2, R ₂ represents 4 carbon atoms. Represents an alkylene group having 4 to 6 carbon atoms or an alkylene group having 4 to 6 carbon atoms interrupted by an oxygen atom;
And when n = 4, R ₂ represents an alkanetetrayl group having 4 to 6 carbon atoms. ).

The compositions of interest are those wherein component (c) has the formula IIa, IIb, IIc or IId

Embedded image

Embedded image

Embedded image And at least one compound represented by the formula:

[0015] Irganox 1098 registered trademark, Irganox registered trademark
1076, registered trademark Irganox 1010, registered trademark Irganox 245,
Irganox 259, Irganox 3114, Irganox 1035, and Irganox 3125 are registered trademarks of Ciba-Geigy.

Preferred compositions comprise as component (c) at least one compound of the formula I (compounds of the formulas IIa, Ia
A compound of Ib, IIc or IId, in particular of formula IIa,
Represents a compound of IIb or IIc, typically a compound of formula IIa. ).

The component (b) of the novel composition, or the phosphite of the formula I, is known and its preparation has been disclosed from the beginning in Example 4 of US Pat. Nos. 4,318,845 and 4,374,219. This phosphite can be obtained by different modifications, in particular U.S. Pat. No. 5,276,076 which discloses a solid amorphous form of the phosphite of formula I,
No. 9 discloses α-crystals of the phosphite of formula I, US Pat. No. 5,326,802 discloses β-crystals of the phosphite of formula I, and US Pat. -Discloses crystals. The phosphites of formula I are commercially available under the registered trademark Irgafos 12 (Ciba-Geigy).

[0018] Component (c) of the novel compositions, or compounds of formula II, are known and some are commercially available. Possible processes for the preparation of the compounds of the formula II can be found in particular in US Pat. Nos. 3,330,859 and 3,609,928.

Polyamides are understood as meaning aliphatic and aromatic polyamides or copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or from their corresponding lactones. Suitable polyamides are, for example, PA6,
PA11, PA12, PA46, PA6.6, PA6.
9, PA6.10 or PA6.12, PA10.1.
2, PA 12.12 and also Trogamid PA-3-T and
Grilamid TR55 type amorphous polyamide. Polyamides of the above type are generally known and commercially available.

The compositions of interest include, as component (a), polyamide 6, polyamide 6.6, polyamide 11 or polyamide 12, or copolymers thereof, especially polyamide 6 or polyamide 6.6, or elastomer-modified polyamide 6 or Polyamide 6.6 blended with polypropylene.

The polyesters may be homo- or copolyesters derived from aliphatic, cycloaliphatic or aromatic dicarboxylic acids and diols or hydroxycarboxylic acids. Aliphatic dicarboxylic acids can contain 2 to 40 carbon atoms, cycloaliphatic dicarboxylic acids can contain 6 to 10 carbon atoms, aromatic dicarboxylic acids can contain 8 to 14 carbon atoms, The group hydroxycarboxylic acid may contain 2 to 12 carbon atoms,
And aromatic and cycloaliphatic hydroxycarboxylic acids can contain from 7 to 14 carbon atoms. Aliphatic diols can contain 2 to 12 carbon atoms, cycloaliphatic diols can contain 5 to 8 carbon atoms, and aromatic diols can contain 6 to 16 carbon atoms. Aromatic diols are understood to mean those in which two hydroxy groups are linked to one or different aromatic hydrocarbon groups. Polyesters can also be used in small amounts, for example 0.1 to 3 mol% based on dicarboxylic acid, of di- or higher functional monomers such as pentaerythritol, trimellitic acid, 1,3,5-tris (hydroxy) benzene,
2,4-dihydroxybenzoic acid or 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane). When the polyester is based on at least three monomers,
The monomers may be randomly dispersed or they may be block polymers. Suitable dicarboxylic acids are linear or branched saturated aliphatic dicarboxylic acids, aromatic dicarboxylic acids and cycloaliphatic dicarboxylic acids.

Suitable aliphatic dicarboxylic acids have 2 carbon atoms.
To 40, typically oxalic, malonic, dimethylmalonic, succinic, pimelic, adipic,
Trimethyladipic, sebacic, azelaic and dimer acids (unsaturated aliphatic carboxylic acids such as the dimer of oleic acid), alkylated malonic acids and succinic acids such as octadecylsuccinic acid.

Suitable cycloaliphatic dicarboxylic acids are: 1,3-cyclobutanedicarboxylic acid, 1,3
-Cyclopentanedicarboxylic acid, 1,3- and 1,4
-Cyclohexanedicarboxylic acid, 1,3- and 1,4
-(Dicarboxymethyl) cyclohexane, 4,4'-
Dicyclohexyl dicarboxylic acid.

Suitable aromatic dicarboxylic acids are: preferably terephthalic acid, isophthalic acid, o-phthalic acid and 1,3-, 1,4-, 2,6- or 2,3-.
7-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid, 4,4′-benzophenonedicarboxylic acid, 1,1,
3-trimethyl-5-carboxyl-3- (p-carboxyphenyl) indane, 4,4'-diphenyletherdicarboxylic acid, bis-p- (carboxyphenyl) methane, or bis-p- (carboxyphenyl) ethane.

Aromatic dicarboxylic acids are preferred, especially terephthalic acid and isophthalic acid and 2,6-naphthalenedicarboxylic acid. Other suitable dicarboxylic acids are those containing a -CO-NH- group, and
-A-2414349.
Dicarboxylic acids containing an N-heterocycle are also suitable,
For example those derived from carboxyalkylated, carboxyphenylated or carboxybenzylated monoamine-s-triazinedicarboxylic acids (DE-A-2121)
184 and 2533675), mono- or bishydantoins, benzimidazolens or halogenated benzimidazolens or parabanic acid. The carboxyalkyl groups in these compounds can contain from 3 to 20 carbon atoms.

Suitable aliphatic diols are linear or branched aliphatic glycols, preferably having 2 carbon atoms in the molecule.
Containing from 1 to 12, most preferably 2 to 6 carbon atoms, including, for example, ethylene glycol, 1,2- and 1,3-propylene glycol, 1,2-, 1,1 3-, 2,3- or 1,
4-butanediol, pentyl glycol, neopentyl glycol, 1,6-hexanediol, 1,12-
Dodecanediol. A suitable cycloaliphatic diol is, for example, 1,4-dihydroxycyclohexane. Other suitable aliphatic diols are typically 1,4-bis (hydroxymethyl) cyclohexane, aromatic-aliphatic diols such as p-xylene glycol or 2,5
-Dichloro-p-xylene glycol, 2,2- (β-
Hydroxyethoxyphenyl) propane, as well as polyoxyalkylene glycols such as diethylene glycol, triethylene glycol, polyethylene glycol or polypropylene glycol. The alkylene diol is preferably linear and preferably contains 2 to 4 carbon atoms.

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

Other suitable aliphatic diols are 2,2-
Β-hydroxyalkylation as exemplified for bis [4 ′-(β-hydroxyethoxy) phenyl] propane,
Preferred is β-hydroxyethylated bisphenol. Other bisphenols are described below.

Other groups of suitable aliphatic diols are described in DE-A-1812003, 234,243.
No. 2, No. 2342372 and No. 2453326
The heterocyclic diols disclosed in US Pat. Exemplified below: N, N′-bis (β-hydroxyethyl-5,5
-Dimethyl) hydantoin, N, N'-bis (β-hydroxypropyl-5,5-dimethyl) hydantoin, methylenebis [N- (β-hydroxyethyl) -5-methyl-5-ethylhydantoin], methylenebis [N-
(Β-hydroxyethyl) -5,5-dimethylhydantoin], N, N′-bis (β-hydroxyethylbenzylimidazolone,-(tetrachloro) benzimidazolone or-(tetrabromo) benzimidazolone. Aromatic diols are mononuclear diphenols, and preferably dinuclear diphenols having a hydroxy group on each aromatic nucleus, where aromatic is preferably an aromatic hydrocarbon group such as a phenylene or naphthylene group. It is to be understood that, besides, for example, hydroquinone, resorcinol or 1,5-, 2,6- and 2,7-dihydroxynaphthalene, bisphenols which can be represented by the formula:

Embedded image

The hydroxy group may be in the m position, but is preferably in the p position. In the above formula, R 'and R "may represent an alkyl group having 1 to 6 carbon atoms, a halogen atom such as a chlorine atom or a bromine atom and preferably a hydrogen atom. A is a direct bond or an oxygen atom, a sulfur atom,- SO
_{-, - SO 2 -,>} CO -, - P (O) (1 carbon atoms
To 20 alkyl)-, an unsubstituted or substituted alkylidene group, a cycloalkylidene group or an alkylene group.

Typical examples of unsubstituted or substituted alkylidene groups are, for example: ethylidene, 1,1- or 2,2-propylidene, 2,2-butylidene,
1,1-isobutylidene group, pentylidene group, hexylidene group, heptylidene group, octylidene group, dichloroethylidene group and trichloroethylidene group. Typical examples of unsubstituted or substituted alkylene groups are methylene, ethylene, phenylmethylene, diphenylmethylene, and methylphenylmethylene. Examples of cycloalkylidene groups are cyclopentylidene, cyclohexylidene, cycloheptylidene and cyclooctylidene.

Typical examples of bisphenols are: bis (p-hydroxyphenyl) ether or bis (p-hydroxyphenyl) thioether, bis (p
-Hydroxyphenyl) sulfone, bis (p-hydroxyphenyl) methane, bis (4-hydroxyphenyl)
-2,2'-biphenyl, phenylhydroquinone, 1,
2-bis (p-hydroxyphenyl) ethane, 1-phenyl-bis (p-hydroxyphenyl) methane, diphenylbis (p-hydroxyphenyl) ethane, diphenylbis (p-hydroxyphenyl) methane, bis (3
5-dimethyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) -p
-Diisopropylbenzene, bis (3,5-dimethyl-
4-hydroxyphenyl) -m-diisopropylbenzene, 2,2-bis (3 ′, 5′-dimethyl-4′-hydroxyphenyl) propane, 1,1- or 2,2-bis (p-hydroxyphenyl) butane 2,2-bis (p-hydroxyphenyl) hexafluoropropane,
1,1-dichloro- or 1,1,1-trichloro-
2,2-bis (p-hydroxyphenyl) ethane, 1,
1-bis (p-hydroxyphenyl) cyclopentane and preferably 2,2-bis (p-hydroxyphenyl) propane (bisphenol A) and 1,1-bis (p-hydroxyphenyl) cyclohexane (bisphenol C).

Suitable polyesters of hydroxycarboxylic acids typically include polycaprolactone, polypivalolactone or polyesters of 4-hydroxycyclohexanecarboxylic acid or 4-hydroxybenzoic acid.

Suitable polymers are also those containing predominantly ester bonds, which may also contain other bonds, for example polyesteramides or polyesterimides.

Polyesters with aromatic dicarboxylic acids, especially polyalkylene terephthalates, have exerted their greatest importance. Therefore, the molding composition according to the invention is characterized in that the polyester has at least 30 mol%, preferably at least 40 mol%, of aromatic dicarboxylic acids, based on the polyester, of at least 30 mol%, preferably at least 40 mol%, preferably at least 40 mol%. Those containing an alkylene diol having 2 to 12 carbon atoms are preferred.

In this case, in particular, the alkylene diol is linear and contains 2 to 6 carbon atoms, typically exemplified by ethylene, trimethylene, tetramethylene or hexamethylene glycol, and aromatic dicarboxylic acids. Is exemplified by terephthalic acid and / or isophthalic acid.

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

Polyketones convert carbon monoxide to, for example,
It is understood to mean a plastics material produced by polymerizing together with the unsaturated hydrocarbons disclosed in PA-0222454 or 0655517.

The above-mentioned advantageous composition comprises, based on the weight of component (a), components (b) and (c) together, from 0.05 to 5%, preferably from 0.1 to 5%.
%, Typically from 0.1 to 2%.

Also preferred are components (b): (c)
Weight ratio of 10: 1 to 1:10, preferably 5: 1
To 1: 5, typically 4: 1 to 1: 2.

In addition to components (b) and (c), the novel compositions may contain additional additives or co-stabilizers, for example:

1. Antioxidants 1.1 Alkylated monophenols , for example 2,6-di-tert-butyl-4-methylphenol, 2-butyl-
4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4
-N-butylphenol, 2,6-di-tert-butyl-4
-Isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4 , 6-Tricyclohexylphenol, 2,6-di-tert-butyl-4
-Methoxymethylphenol, 2,6-dinonyl-4-
Methylphenol, 2,4-dimethyl-6- (1′-methyl-undec-1′-yl) -phenol, 2,4-
Dimethyl-6- (1'-methyl-heptadec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyl-tridec-1'-yl) -phenol and mixtures thereof.

1.2. Alkylthiomethylphenol,
For example, 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4-di-octylthiomethyl-6-
Methylphenol, 2,4-di-octylthiomethyl-
6-ethylphenol and 2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3 Hydroquinone and alkylated hydride
Roquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6
-Diphenyl-4-octadecyloxyphenol,
2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert- Butyl-4-hydroxyphenyl stearate,
Bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4 Tocophenols such as α-tocophenol, β-tocophenol, γ-tocophenol, δ-tocophenol and mixtures thereof (vitamin E).

1.5 Hydroxylated thiodiphenyl ether
Ether, e.g., 2,2'-thiobis (6-tert-butyl -
4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl- 2-methylphenol), 4,4 '
-Thio-bis (3,6-di-secondary-amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) -disulfide.

1.6 Alkylidenebisphenols , such as 2,2′-methylene-bis (6-tert-butyl-4-
Methylphenol), 2,2'-methylene-bis (6-
Tert-butyl-4-ethylphenol), 2,2′-methylene-bis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2′-methylene-bis (4-
Methyl-6-cyclohexylphenol), 2,2'-
Methylene-bis (6-nonyl-4-methylphenol), 2,2'-methylene-bis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4
6-di-tert-butylphenol), 2,2'-ethylidene-bis (6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis [6- (α-methylbenzyl) -4- Nonylphenol], 2,2'-methylene-bis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylene-bis (2,6
-Di-tert-butylphenol), 4,4'-methylene-
Bis (6-tert-butyl-2-methylphenol), 1,
1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-
5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-
Hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis (3 '-Tert-butyl-
4'-hydroxyphenyl) butyrate], bis (3-
Tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-
2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1
-Bis (3,5-dimethyl-2-hydroxyphenyl)
Butane, 2,2-bis (3,5-di-tert-butyl-4-
(Hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4
-N-dodecyl mercaptobutane, and 1,1,5,
5-tetra- (5-tert-butyl-4-hydroxy-2-
Methylphenyl) pentane.

1.7. O-, N- and S-benzyl
Compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate, tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) -amine, bis (4
-Tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) -sulfide and isooctyl-3,5-di-tert. Butyl-4-hydroxybenzyl-mercaptoacetate.

1.8. Hydroxybenzylated maloney
E.g., dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) -malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methyl) Benzyl) -malonate, di-dodecylmercaptoethyl-2,2-bis (3,5-di-
Tert-butyl-4-hydroxybenzyl) -malonate,
And bis- [4- (1,1,3,3-tetramethylbutyl) -phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -malonate.

1.9. Hydroxybenzyl aromatic compound
Object, for example 1,3,5-tris (3,5-di - tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di - tert Butyl-
4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene and 2,4,6-tris (3,5-di-
Tert-butyl-4-hydroxybenzyl) -phenol.

1.10. Triazine compounds, for example,
2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5
-Triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino)
-1,3,5-triazine, 2-octylmercapto-
4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6
-Tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -Isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -isocyanurate, 2,4,6-tris (3,5
-Di-tert-butyl-4-hydroxyphenylethyl)-
1,3,5-triazine, 1,3,5-tris (3,5
-Di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine,
3,5-Tris (3,5-dicyclohexyl-4-hydroxybenzyl) -isocyanurate.

1.11. Benzylphosphonates such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di -Tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-
Ca salt of 4-hydroxy-3-methylbenzylphosphonate and 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.

1.12. Acylaminophenols such as 4-hydroxyanilide laurate, 4-hydroxyanilide stearate, N- (3,5-carbamic acid)
Di-tert-butyl-4-hydroxyphenyl) octyl ester.

1.13. β- (3,5-di-tert-butyl
(4-Hydroxyphenyl) propionic acid
Esters with polyhydric or polyhydric alcohols such as methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, Diethylene glycol, triethylene glycol, pentaerythritol,
Tris (hydroxyethyl) isocyanurate, N,
N'-bis (hydroxyethyl) oxalic acid diamide, 3
-Thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane,
4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.14. β- (5-tert-butyl-4-
(Hydroxy-3-methylphenyl) propionic acid
Esters with monohydric or polyhydric alcohols such as methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiol Diethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate,
N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,6
7-trioxabicyclo [2.2.2] octane.

1.15. β- (3,5-di-cyclohe
Xyl-4-hydroxyphenyl) propionic acid
Esters with mono- or polyhydric alcohols such as methanol, ethanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol , Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate,
N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,6
7-trioxabicyclo [2.2.2] octane.

1.16. 3,5-di-tert-butyl-4
The following monovalent or polyvalent alky!
Esters with coal, such as methanol, ethanol, octadecanol, 1,6-hexanediol,
1,9-nonanediol, ethylene glycol, 1,2
-Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, -Thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.17. β- (3,5-di-tert-butyl
Amides of l-4-hydroxyphenyl) propionic acid such as N, N'-bis (3,5-di-tert-butyl-4-
(Hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-
(Hydroxyphenylpropionyl) trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.

1.18. Ascorbic acid (vitamin C)

1.19 Amine antioxidants such as N, N′-diisopropyl-p-phenylenediamine, N, N′-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-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di (2 -Naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p
-Phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N-
(1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-
p-phenylenediamine, 4- (p-toluenesulfonamido) diphenylamine, N, N'-dimethyl-N,
N'-secondary butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine such as p, p ' -Di-tert-butyl-
Octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di (4-
Methoxyphenyl) amine, 2,6-ditert-butyl-butyl-4-dimethylaminomethylphenol, 2,4 ′
-Diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-
4,4'-diaminodiphenylmethane, 1,2-di [(2-methylphenyl) amino] ethane, 1,2-di (phenylamino) propane, (o-tolyl) biguanide, di [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, mixtures of mono- and dialkylated tert-butyl / tert-octyldiphenylamine, mixtures of mono- and dialkylated isopropyl / isohexyldiphenylamine , Mono- and dialkylated tert-butyldiphenylamine, mixtures of 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, N-allylphenothiazine, N, N, N ', N'-
Tetraphenyl-1,4-diaminobut-2-ene,
N, N-bis (2,2,6,6-tetramethylpiperidi-4-yl-hexamethylenediamine, bis (2,2,
6,6-tetramethylpiperidi-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethylpiperidin-4
-All.

[0061] 2. UV absorbers and light stabilizers 2.1. 2- (2'-hydroxyphenyl) benzoto
Liazol , for example, 2- (2′-hydroxy-5′-
Methylphenyl) benzotriazole, 2- (3 ′,
5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-
Hydroxy-5 ′-(1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ′,
5'-di-tert-butyl-2'-hydroxyphenyl)-
5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5
Chlorobenzotriazole, 2- (3'-secondary butyl-
5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3 ', 5'
-Di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole; 2- (3'- Tert-butyl-2'-hydroxy-5 '-(2'-octyloxycarbonylethyl)
Phenyl) -5-chlorobenzotriazole, 2-
(3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-
Tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-methoxy Carbonylethyl) phenyl)
Benzotriazole, 2- (3'-tert-butyl-2'-
Hydroxy-5 '-(2-octoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5'-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) Benzotriazole, 2- (3-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, and 2- (3'-tert-butyl-2'-hydroxy-5'-
A mixture of (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2′-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6
-Benzotriazol-2-ylphenol]; 2-
[3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] transesterification product of benzotriazole with polyethylene glycol _{300; [R-CH 2 CH} 2 -COO (CH 2 ) _3- ]
_2- (wherein R = 3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-yl-phenyl, 2- [2′-hydroxy-3 ′-(α, α-dimethylbenzyl) -5 ′-(1,1,3,3-tetramethylbutyl) -phenyl] benzotriazole.);
2- [2'-hydroxy-3 '-(1,1,3,3-tetramethylbutyl) -5'-(α, α-dimethylbenzyl) -phenyl] benzotriazole.

2.2. 2-hydroxy-benzopheno
Emissions, such as 4-hydroxy -, 4-methoxy -, 4-octoxy -, 4-decyloxy -, 4-dodecyloxy -, 4-benzyloxy -, 4,2 ', 4'-trihydroxy - or 2'Hydroxy-4,4'-dimethoxy derivatives.

2.3. Substituted and unsubstituted benzoic
Esters of acids such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl
Salicylate, dibenzoylresorcinol, bis (4
-Tert-butylbenzoyl) resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl =
3,5-di-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 , such as ethyl α
-Cyano-β, β-diphenyl-acrylate, isooctyl α-cyano-β, β-diphenyl-acrylate, methyl α-carbomethoxy-cinnamate, methyl α-cyano-β-methyl-p-methoxy-cinnamate, butyl α- Cyano-β-methyl-p-methoxy-cinnamate, methyl α-carbomethoxy-p-methoxycinnamate, and N- (β-carbomethoxy-β-
(Cyanovinyl) -2-methylindoline.

2.5. Nickel compounds , such as 2,
Nickel complexes of 2'-thiobis- [4- (1,1,3,3-tetramethylbutyl) -phenol], for example 1:
1 or 1: 2 complexes, optionally with other ligands such as n-butylamine, triethanolamine or N-cyclohexyl-di-ethanolamine, nickel dibutyldithiocarbamate, 4-hydroxy-3 Monoalkyl esters of 5,5-di-tert-butylbenzylphosphonic acid such as nickel salts of methyl or ethyl esters, ketoximes such as 2-hydroxy-4
Nickel complexes of -methyl-phenylundecylketoxime and nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with other ligands.

2.6. Sterically hindered amines such as bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (2,2,6,6-tetramethylpiperidyl)
Succinate, bis (1,2,2,6,6-pentamethylpiperidyl) sebacate, bis (1,2,2,6,6
-Pentamethylpiperidyl) n-butyl-3,5-di-
Tert-butyl-4-hydroxybenzylmalonate, 1-
A condensation product of (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, N, N′-bis (2,2,6,6-tetramethyl-4 -Piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-
Tris (2,2,6,6-
Tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-
Piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1 '-(1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-
Benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidyl) -2- n-butyl-2- (2-hydroxy-3,5-di-tert-butyl-benzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [ 4.5] Decane-2,
4-dione, bis (1-octyloxy-2,2,6,
6-tetramethylpiperidyl) sebacate, bis (1-
Octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, N, N'-bis (2,2,6,6
-Tetramethyl-4-piperidyl) -hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,3
Condensation product with 5-triazine, 2-chloro-4,6-
Di (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-
Condensation product of bis (3-aminopropylamino) ethane, 2-chloro-4,6-di (4-n-butylamino-
1,2,2,6,6-pentamethylpiperidyl) -1,
Condensation product of 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-1- (1,2,2,6,6-pentamethyl-4
-Piperidyl) -pyrrolidine-2,5-dione, 4-hexadecyloxy and 4-stearyloxy-2,2.
A mixture of 6,6-tetramethylpiperidine, N, N'-
Condensation product of bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine with 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2- Bis (3-aminopropylamino)
Condensation products of ethane and 2,4,6-trichloro-1,3,5-triazine, and 4-butylamino-2,2,
6,6-tetramethylpiperidine (CAS registration number [1
36504-96-6], N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-
Piperidyl) -4-piperidyl) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4,5] Decane, 7,7,9,9-tetramethyl-
2-cycloundecyl-1-oxa-3,8-diaza-
The reaction product of 4-oxospiro [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) hexamethylenediamine,
Diester of -methoxymethylenemalonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxy-4- (2,
2,6,6-tetramethyl-4-piperidyl)] siloxane, maleic anhydride-α-olefin copolymer and 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6 Reaction product with 6-pentamethyl-4-aminopiperidine.

2.7. Oxamide , for example, 4,4'-
Dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2 '
-Didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethoxanilide, N, N'-
Bis (3-dimethylaminopropyl) oxamide, 2-
Ethoxy-5-tert-butyl-2'-ethyloxanilide and the compound and 2-ethoxy-2'-ethyl-5.
Mixtures with 4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and o-
And mixtures of p-ethoxy-disubstituted oxanilides.

2.8. 2- (2-hydroxyphenyl)
L) -1,3,5-triazine , for example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl)
-1,3,5-triazine, 2- (2-hydroxy-4
-Octyloxyphenyl) -4,6-bis (2,4-
Dimethylphenyl) -1,3,5-triazine, 2-
(2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6 (2,4-dimethylphenyl)-
1,3,5-triazine, 2- (2-hydroxy-4-
Octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethyl Phenyl) -1,3,5-triazine. 2- [2-hydroxy-4- (2-hydroxy-3
-Butyloxy-propyloxy) phenyl] -4,6
-Bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl]
-4,6-bis (2,4-dimethylphenyl) -1,
3,5-triazine.

[0069] 3. Metal deactivators such as N, N'-
Diphenyl oxalic acid diamide, N-salicyl-N'-
Salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2,4-triazole, bis (benzylidene) oxalic acid dihydrazide, oxanilide, isophthalic acid dihydrazide, sebacic acid-bis-phenylhydrazide, N, N′-diacetal-adipate dihydrazide, N, N′-bis-salicyloyl-oxalic acid Dihydrazide, N, N'-bis-salicyloyl-thiopropionic dihydrazide.

[0070] 4. Phosphites and phosphonites ,
For example, triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,
4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2
4-di-tert-butylphenyl) -pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-)
Methylphenyl) -pentaerythritol diphosphite, bis-isodecyloxy-pentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) -pentaerythritol diphosphite, bis (2 4,6-tri-tert-butyl-butylphenyl) -pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylenediphosphonite, 6 -Isooctyloxy-2,
4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphosine, 6-fluoro-2,4,8,10-tetra-tert-butyl- 12
-Methyl-dibenz [d, g] -1,3,2-dioxaphosphine, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bis (2,4-di-
Tert-butyl-6-methylphenyl) ethyl phosphite.

[0071] 5. Hydroxylamines , such as N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-diethylhydroxylamine, derived from hydrogenated tallowamine;
N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N
-Hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine.

6 Nitrones, for example N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone, N-lauryl- derived from hydrogenated tallowamine.
Alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone, N-hexadecyl-alpha-pentadecyl nitrone, N-octadecyl-alpha-heptadecyl nitrone, N-hexadecyl-alpha-heptadecyl nitrone, N-octadecyl- Alpha-pentadecyl nitrone, a nitrone derived from N, N-dialkylhydroxyamine.

[0074] 7. Thio-synergists such as dilauryl thiodipropionate or distearyl thiodipropionate.

[0074] 8. Peroxide scavenger , for example β
Esters of thiodipropionic acid, such as lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or zinc salts of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis (β-dodecylmercapto ) Propionate.

9. Polyamide stabilizers , for example copper salts in combination with iodides and / or phosphorus compounds, and salts of divalent manganese.

10. Basic co-stabilizers such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal and alkaline earth metal salts of higher fatty acids, such as Ca stearate, Zn stearate, Mg behenate, Mg stearate, Na ricinoleate and K palmitate, catechol antimony salt and catechol tin salt.

11. Nucleating agents , for example inorganic substances, for example metal oxides such as talc, titanium dioxide or magnesium oxide, preferably alkaline earth metal phosphates, carbonates or sulphates; organic compounds, for example mono- or polycarboxylic acids and Salts thereof, for example, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymerizable compounds such as ionic copolymers ("ionomers").

12. Fillers and reinforcing agents such as calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and other natural products Powder and fiber, synthetic fiber.

13. Other additives , such as plasticizers, lubricants, emulsifiers, pigments, rheology add
itives), catalysts, flow control agents, brighteners, flame retardants, antistatic agents and blowing agents.

14. Benzofuranone or indolino
Down, for example, U.S. Pat invention herein (US-A-) No. 432
No. 5863, No. 4338244, No. 517531
No. 2, No. 5216052, No. 5252643,
DE-A 43 166 A1
No. 11, No. 4,316,622, No. 4,316,876
No., EP-A-058
No. 9839 or No. 0591022 or 3- [4- (2-acetoxyethoxy)
Phenyl] -5,7-di-tert-butyl-benzofurano-
2-one, 5,7-di-tert-butyl-3- [4- (2-
Stearoyloxyethoxy) phenyl] benzofurano-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofurano-2-one], 5 , 7-di-tert-butyl-3
-(4-ethoxyphenyl) benzofurano-2-one,
3- (4-acetoxy-3,5-dimethylphenyl)-
5,7-di-tert-butyl-benzofurano-2-one, 3
-(3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butyl-benzofurano-2-one.

Except for the benzofuranones mentioned in clause 14, the co-stabilizer is added, typically at a concentration of 0.01 to 10% by weight, based on the total weight of the material to be stabilized.

Other preferred compositions comprise, besides component (a), a compound of the formula I, other additives, preferably phenolic antioxidants, light stabilizers and / or processing stabilizers.

Particularly preferred additives are phenolic antioxidants (item 1 in the table) and sterically hindered amines (item 2. in the table).
6), phosphite and phosphonite (item 4 in the table)
And a peroxide scavenger (item 8 in the table).

Other additives (stabilizers) which are particularly preferred are also benzofurano-2-ones, such as, in particular, US-A-
4325863, US-A-4338244, US-A
-5175312, US-A-5216052, US-
A-5252643, DE-A-4316611, DE
-A-4316622, DE-A-4316876, E
PA-058939 and EP-A-059110
2.

A specific example of benzofuran-2-one is represented by the following formula:

Embedded image Wherein R ′ ₁₁ represents an unsubstituted or substituted carbocyclic aromatic or heterocyclic aromatic system, R ′ ₁₂ represents a hydrogen atom, R ′ ₁₄ represents a hydrogen atom, and 1 to 12 Represents an alkyl group having a carbon atom, a cyclopentyl group, a cyclohexyl group or a chlorine atom, wherein R ′ ₁₃ has the meaning of R ′ ₁₂ or R ′ ₁₄ or

Embedded image Wherein R ′ ₁₆ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by an oxygen atom or a sulfur atom. A dialkylaminoalkyl group having a total of 3 to 16 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group or a phenyl group substituted by a 1 to 3 alkyl group having a total of at most 18 carbon atoms And s represents 0, 1 or 2, and the substituents R ′ ₁₇ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, A phenyl group substituted by one or two alkyl groups having at most 16 carbon atoms, -C
_{2 H 4 OH, -C 2 H} 4 -O-C t H 2t + 1 or the following formula

Embedded image In represented together with the radical or a nitrogen atom to which they are attached form a piperidine or morpholine group; t is 1 to represent 18, R _'20 represents a hydrogen atom, 1 to 22
Alkyl groups having 5 carbon atoms or 5 to 12
A represents a cycloalkyl group having 2 carbon atoms, wherein A is 2 interrupted by a nitrogen, oxygen or sulfur atom
Represents an alkylene group having from 22 to 22 carbon atoms,
R ′ ₁₈ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, and a group having at most 16 carbon atoms in total.
Or two alkyl phenyl group substituted by a group, or a benzyl group, R _'19 is 1 to 18
Represents an alkyl group having carbon atoms, D is -O-,
-S -, - SO -, - SO 2 - or -C (R _'21)
And the substituents R ′ ₂₁ each independently represent a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, or two R ′ _{21 taken} together form 1 to 16 carbon atoms. And R ′ ₂₁ further comprises a phenyl group or

Embedded image (Wherein, s, R ′ ₁₆ and R ′ ₁₇ represent the same meaning as described above), and E represents the following formula:

Embedded image (Wherein, R ′ ₁₁ , R ′ ₁₂ and R ′ ₁₄ represent the same meaning as described above), and R ′ ₁₅ represents a hydrogen atom,
An alkyl group having 1 to 20 carbon atoms, a cyclopentyl group, a cyclohexyl group, a chlorine atom or

Embedded image (Wherein, R ′ ₁₆ and R ′ ₁₇ represent the same meaning as described above), or R ′ ₁₅ and R ′ ₁₄ together form a tetramethylene group. ] It is a compound represented by these.

A preferred benzofuran-2-one is R ′
₁₃ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a chlorine atom or

Embedded image Or (wherein, s _{is, R '16, R' 17} , D and E represent. The meaning of the) -D-E represents a group represented by,
R _'16 is preferably a hydrogen atom, benzofuran-2-one represents an alkyl group, a cyclopentyl group or cyclohexyl group having 1 to 18 carbon atoms.

Preferred benzofuran-2-ones are also
R ′ ₁₁ represents a phenyl group or a phenyl group substituted by one or two alkyl groups having at most 12 carbon atoms, R ′ ₁₂ represents a hydrogen atom,
R _'14 represents an alkyl group having a hydrogen atom or 1 to 12 carbon atoms, R' ₁₃ represents a hydrogen atom, alkyl having 1 to 12 carbon atoms, the formula

Embedded image Or represents -D-E, R _'15 represents a hydrogen atom or a
An alkyl group having from 20 to 20 carbon atoms,

Embedded image Or R ′ ₁₅ and R ′ ₁₄ together form a tetramethylene group, s, R ′ ₁₆ , R ′ ₁₇ , D
And E are benzofuran-2-one having the above-mentioned meaning.

[0088] Also especially benzofuran-2-of interest, R _'13 represents a hydrogen atom, 1 to represent an alkyl or -D-E having 12 carbon atoms, R' ₁₂ and R _'14 are each independently of one another, to a hydrogen atom or 1 to an alkyl group having 4 carbon atoms, R _'15
Represents an alkyl group having 1 to 20 carbon atoms, and D and E are benzofuran-2-one having the above-mentioned meaning.

[0089] the last one especially of interest, R _'13
Alkyl represents a group or -D-E, R _'12 and R' ₁₄ represents a hydrogen atom, and R _'15 is an alkyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms, represents cyclopentyl or cyclohexyl, D is _{-C (R '2 1) 2} - represents a group represented by, and E is the following formula

Embedded image Wherein the substituents R ′ ₂₁ are the same or different and represent an alkyl group having 1 to 4 carbon atoms, and R ′ ₁₁ , R ′ ₁₂ , R ′ ₁₄ and R ′ ₁₅ Is benzofuran-2- which represents the above-mentioned meaning.
Is on.

The amount of benzofuran-2-one additionally used can vary widely. The novel composition typically contains it from 0.0001 to 5% by weight, preferably from 0.001 to 2% by weight, most preferably from 0.01 to 2% by weight.

Components (b) and (c) and the other additives are typically prepared by known methods before or during molding or by dissolving or dispersing components (a) and (b) It is incorporated into component (a) [polyamide, polyester or polyketone] by application to (a) followed by evaporation of the solvent. Components (b) and (c) are also added to the material to be stabilized in the form of a masterbatch containing these compounds, typically at a concentration of 2.5 to 25% by weight. Component (b)
And (c) can also be added before or during polymerization or before crosslinking.

Components (b) and (c) can be incorporated in component (a) to be stabilized in pure form or encapsulated in wax, oil or polymer.

Components (b) and (c) can also be sprayed onto component (a) to be stabilized. They can dilute other additives (for example the customary additives mentioned above) or their melts, so that they can be sprayed together with these additives on component (a) to be stabilized. Spray application during the deactivation of the polymerization catalyst is particularly advantageous, in which case the steam used for the deactivation can also be used for the spraying.

A polyamide stabilized by this method,
Polyesters and polyketones are used in a wide variety of forms, typically as binders, adhesives or cement binders for films, fibers, filaments, molded articles, profiles or paints.

The components (b) and (c) are particularly suitable as processing stabilizers (heat stabilizers). For this purpose, they are added to component (a) before or during their processing.

Accordingly, a preferred embodiment of the present invention is a compound of formula (I) as a stabilizer for polyamides, polyesters or polyketones against oxidative, thermal or light-induced degradation, preferably as a processing stabilizer (heat stabilizer). I
And the use of at least one compound of the formula II.

Components (b) and (c) are characterized by their favorable color behavior, ie, low discoloration of the polyamides, polyesters and polyketones during processing.

Accordingly, the present invention relates to a method for stabilizing a polyamide, polyester or polyketone against oxidative, thermal or light-induced degradation, which comprises converting a phosphite of the formula I and at least one compound of the formula II. Consists of mixing into them or applying on them.

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

A preferred stabilizer mixture comprises component (i):
The weight ratio of (ii) is from 10: 1 to 1:10, preferably from 5: 1 to 1: 5, typically from 4: 1 to 1: 2.
It is something that is.

Preferred compounds of the formula II for use as stabilizers, for the stabilization process and for the stabilizer mixtures are the same as those described for compositions with polyamides, polyesters or polyketones.

The stabilizer mixture of components (i) and (ii) is called an LC blend (low color blend). They are characterized by good storage stability, low volatility and excellent flow properties. The LC blends listed in Table 1 are particularly preferred.

[Table 1] a) Irgafos 12 is consistent with the compound of formula I. b) Irganox 1010® is consistent with the compound of formula IIc. c) Irganox 3114 is consistent with the compound of Formula IIg. d) The trademark Irganox 1098 is consistent with the compound of formula IIa. e) The registered trademark Irganox 1076 is consistent with the compound of formula IIb.

The present invention is further described in detail by the following examples. Parts and percentages are by weight.

EXAMPLE 1 Stabilization of Polyamide 6 100 parts of unstabilized polyamide 6 granules (Ultramide B3 provided by BASF) are ground by cryogenic griding and powdered. The stabilizers of Table 2 were added. The mixture was mixed for 2 hours using a Henschel mixer.
The powder so obtained was dried at 80 ° C. for 6 hours, extruded at up to 240 ° C. in an extruder (Berstoff type) and granulated. The granules so obtained were molded on an injection molding machine at a maximum of 240 ° C. to give 1.0 mm thick dumbbells and 2.0 mm thick plates.

The dumbbells were aged at 140 ° C. in a circulating air oven. The progress of aging was observed at intervals of one to three days while creating a forced elongation diagram. The end point was defined as the time until the residual strain dropped to 50% of the initial value. The longer the time, the better the stabilization. The results are summarized in Table 2.

The plate was heated at 80 ° C. for 1 hour in a circulating air oven.
Aged for 500 hours. The yellowness index (YI) of these plates was measured according to ASTM D 1925-70. A lower yellowness index indicates less discoloration and a higher yellowness index indicates greater discoloration of the sample. The less discoloration, the more effective stabilizer mixture. The results are summarized in Table 2.

[Table 2] a) Irgafos 168 (Ciba Geigy) is a tris (2,4-di-tert-butylphenyl) phosphite. b) The registered trademark Irganox 1098 (manufactured by Ciba Geigy) has the following formula IIa

Embedded image N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine (compound of formula IIa) represented by the formula: c) The registered trademark Irgafos12 (manufactured by Ciba Geigy) has the following formula I

Embedded image 2,2 ′, 2 ″ -nitrilo [triethyl-
Tris (3,3 ', 5,5'-tetra-tert-butyl-
1,1′-biphenyl-2,2′-diyl) phosphite]. Chemical abstract registration number: 804
And a compound represented by the following formula I:

From the results in Table 2, the novel stabilizer mixture (Example 1c) was obtained from the known stabilizer mixture (Example 1b).
It is more effective in the market.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C08K 5/527 C08K 5/527 C08L 67/00 C08L 67/00 67/02 67/02 73/00 73/00 77/02 77/02 77/06 77/06 C09K 15/32 C09K 15/32 D // C07C 235/44 9547-4H C07C 235/44 C07D 251/34 C07D 251/34 G

Claims (15)

[Claims] 1. a) a polyamide, polyester or polyketone which is susceptible to oxidative, thermal or light-induced degradation b) the following formula I: ## STR1 ## And c) at least one of the following formulas II: Wherein R ₁ represents an alkyl group having 1 to 4 carbon atoms, n represents 1, 2, 3 or 4, X represents a methylene group, and the following formula: Y represents an oxygen atom or —NH—, and when n = 1, X represents the following formula: The stands, Y is bonded to R _2, and R ₂ represents an alkyl group having 1 -C 25 atoms, and for n = 2 X the following formula: 5] The stands, Y is bonded to R _2, and R ₂ is either an alkylene group of alkylene 2 to 12 carbon atoms, C 4 -C interrupted by an oxygen atom or a sulfur atom 12, or When Y represents -NH-, R
₂ further represents a direct bond, and when n = 3, X is a methylene group or the following formula: The represents an ethylene group in the formula is bonded to R _2, and R ₂ is the following formula: 7] And when n = 4, X is the following formula: The stands, Y is bonded to R _2, and R ₂ represents a alkanetetrayl group 10 from 4 carbon atoms. A composition comprising the compound represented by the formula: 2. A composition according to claim 1, wherein component (c) is at least one compound of the formula II, wherein n = 1 and R ₂ represents an alkyl group having 1 to 20 carbon atoms. Composition. 3. Component (c) is at least one compound of formula II, wherein n = 2, R ₂ is interrupted by an alkylene group having 2 to 8 carbon atoms, an oxygen atom or a sulfur atom. When C 4 -C 8 alkylene or Y represents —NH—, R ₂ further represents a direct bond, and when n = 4, R ₂ represents C 4 -C 8 alkanetetrane. 2. The composition according to claim 1, which represents an yl group. 4. Component (c) is at least one compound of formula II wherein R ₁ is methyl or tert-butyl, n is 1, 2 or 4, and X is Embedded image Y represents an oxygen atom or -NH-, and when n = 1, R ₂ represents an alkyl group having 14 to 18 carbon atoms, and when n = 2, R ₂ represents 4 carbon atoms. Represents an alkylene group having 4 to 6 carbon atoms or an alkylene group having 4 to 6 carbon atoms interrupted by an oxygen atom;
And when n = 4, R ₂ represents an alkanetetrayl group having 4 to 6 carbon atoms. The composition according to claim 1, wherein 5. Component (c) has the following formula IIa, IIb, I
Ic or IId Embedded image The composition according to claim 1, which is at least one compound represented by the following formula: 6. The composition according to claim 5, wherein component (c) is a compound of formula IIa, IIb or IIc. 7. The composition according to claim 1, wherein the polyamide is polyamide 6, polyamide 6.6, polyamide 11 or polyamide 12, or a copolymer thereof. 8. The polyester according to claim 1, wherein the polyester is PET, PETG or PBT, or a copolymer thereof.
A composition as described. 9. The composition of claim 1, wherein components (b) and (c) are present together in an amount of 0.05 to 5% based on the weight of component (a). 10. The weight ratio of component (b) :( c) is 10:
The composition according to claim 1, wherein the ratio is 1 to 1:10. 11. The composition according to claim 1, which further comprises, besides components (b) and (c), further additives. 12. The composition according to claim 11, which comprises as additional additives phenolic antioxidants, light stabilizers and / or processing stabilizers. 13. An additional additive comprising at least one
2. Compounds of the benzofuran-2-one type.
The composition of claim 1. 14. A stabilizer mixture comprising (i) a phosphite of the formula I according to claim 1 and (ii) at least one compound of the formula II. 15. The weight ratio of component (i) :( ii) is 1
15. Stabilizer mixture according to claim 14, wherein the ratio is from 0: 1 to 1:10.