GB2347427A - Stabilizing polyolefins with a mixture comprising a sterically hindered amine - Google Patents

Abstract

Polyolefins are stabilized with a mixture comprising<BR> (A) a sterically hindered amine selected from compounds 13,14,36-a, 36-d, 96-I, 96-II, 100-A, 101-1, 105 and 106 as defined in the specification,<BR> (B) an organic or inorganic salt of Ca and<BR> (C) an organic or inorganic salt of Mg or an organic or inorganic salt of Zn,;<BR> with the proviso that the polyolefin is polypropylene when component (A) is the compound 96-I, 96-II or 100-A.

Description

Stabilizer mixtures The present invention relates to a stabilizer mixture containing a sterically hindered amine compound, a Ca compound and an Zn or Mg compound, the use of this mixture for stabilizing a polyolefin against degradation induced by light, heat or oxidation and the polyolefin thus stabilized.

The stabilization of polyolefins is described in numerous publications, for example in US-A-4,929,652, US-A-5,025,051, US-A-5,037,870, EP-A-276,923, EP-A-290,388, EP-A-429, 731, EP-A-468, 923, EP-A-565,184, EP-A-690, 094, GB-A-2, 252,324, DE-A-19, 545,896 (Derwent 96-278,994/29; Chemical Abstracts 125: 116779q), WO-A-95/25, 767 and Chemical Abstracts 106: 197407z In more detail, the present invention relates to a stabilizer mixture containing (A) a sterically hindered amine compound, (B) an organic salt of Ca or an inorganic salt of Ca and (C) an organic salt of Mg, an inorganic salt of Mg, an organic salt of Zn or an inorganic salt of Zn ; with the proviso that component (C) is Mg-hydroxide-carbonate, Zn-hydroxide-carbonate or dolomite, when component (B) is calcium stearate.

Component (C) is in particular Mg-hydroxide-carbonate, Zn-hydroxide-carbonate or dolomite, when component (B) is an organic salt of Ca.

The sterically hindered amine is preferably a compound containing at least one group of the formula (I) or (II)

in which G is hydrogen or methyl, and G, and G2, independently of one another, are hydrogen, methyl or together are a substituent =0.

More detailed examples of sterically hindered amines are described below under classes (a') to (i').

(a') A compound of the formula (la)

in which n, is a number from 1 to 4, G and G,, independently of one another, are hydrogen or methyl, Gn is hydrogen, O, hydroxyl, C,-C, 8alkyl, C3-C8alkenyi, C3-C8alkynyl, CrC, 2aralkyi, C1-C18alkoxy, C5-C8cycloalkoxy, C7-C9phenylalkoxy, C1-C8alkanoyl, C3-C5alkenoyl, C1-C18alkanoyloxy, glycidyl or a group of the formula-CH2CH (OH)-Z, in which Z is hydrogen, methyl or phenyl, G11 preferably being H, C,-C4alkyl, allyl, benzyl, acetyl or acryloyl, and Gt2, if n, is 1, is hydrogen, C1-C18alkyl which is uninterrupted or interrupted by one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl, a monovalent radical or an aliphatic, cycloaliphatic, araliphatc, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic carboxylic aad having 7 to 15 carbon atoms, or an a,-unsaturated carboxylic acid having 3 to 5 carbon atoms or of an aromatic carboxylic acid having 7 to 15 carbon atoms, where each carboxylic acid can be substituted in the aliphatic, cycloaliphatic or aromatic moiety by 1 to 3-COOZ, 2 groups, in which Z, 2 is H, C,-C20alkyl, C3-Cl2alkenyl, CsCC7cycioalkyl, phenyl or benzyl, G12, if n, is 2, is C2-C12alkylene, C4-C12alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphoruscontaining acid or a divalent silyl radical, preferably a radical of an aliphatic dicarboxyiic acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic dicarboxytic acid having 8-14 carbon atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 carbon atoms, where each dicarboxyiic acid may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by one or two-COOZ, groups, G12, if n, is 3, is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, which may be substituted in the aliphatic, cycloaliphatic or aromatic moiety by -COOZt2, of an aromatic tricarbamic acid or of a phosphorus-containing acid, or is a trivalent silyl radical, and G, 2, if n, is 4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxy4ic acid.

The carboxyfic acid radicals mentioned above are in each case taken to mean radicals of the formula (-CO) xR, where x is as defined above, and the meaning of R arises from the definition given.

Alkyl with up to 20 carbon atoms is, for example, methyl, ethyl, n-propyl, n-butyi, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyi, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Cg-Ceatkeny) Gn can be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, or 4-tert-butyl-2-butenyl.

C3-C8alkynyl G"is preferably propargyi.

C7-C12aralkyl G11 is, in particular, phenethyl, especially benzyl, C,-C, salkoxy G"is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy. C6-C, 2alkoxy, in particular heptoxy and octoxy, is preferred.

Cs-Cgcydoafkoxy G11 is, for example, cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. CrC8cycloalkoxy, in particular cyclopentoxy and cyclohexoxy, is preferred.

CrCgphenylalkoxy is, for example, benzyloxy.

C,-C8alkanoyl G11 is, for example, formyl, propionyl, butyryl, octanoyi, but preferably acetyl and C3-Csalkenoyl G"is in particufaracrytoyf.

C1-C18alkanoyloxy G11 is, for example, formyloxy, acetyloxy, propionyloxy, butyryloxy, valeryloxy, lauroyloxy, palmitoyloxy and stearoyloxy.

Examples of several G, 2 radicals are given below.

If G12 is a monovalent radical of a carboxylic acid, it is, for example, an acetyl, caproyl, stearoyl, acryloyl, methacryloyl, benzoyl or ss-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.

If G, 2 is a monovalent silyl radical, it is, for example, a radical of the formula - (CjH2j)-Si (Z') 2Z", in which j is an integer in the range from 2 to 5, and Z'and Z", independently of one another, are C,-C4alkyi or C,-C4alkoxy.

If G, 2is a divalent radical of a dicarboxylic acid, it is, for example, a malonyl, succinyl, glutaryl, adipoyl, suberoyl, sebacoyl, maleoyi, itaconyl, phthaloyl, dibutylmalonyt, dibenzylmalonyl, butyl (3,5-di-tert-butyl-4-hydroxybenzyl) malonyl or bicycloheptenedicarbonyl radical or a group of the formula

If G, 2 is a trivalent radical of a tricarboxylic acid, it is, for example, a trimellitoyl, citryl or nitrilotriacetyl radical.

If G12 is a tetravalent radical of a tetracarboxylic acid, it is, for example, the tetravalent radical of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid. if G, 2 is a divalent radical of a dicarbamic acid, it is, for example, hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radical.

Preference is given to compounds of the formula (la) in which G and G, are hydrogen, Gn is hydrogen or methyl, ni is 2 and G 12 is the diacyl radical of an aliphatic dicarboxyiic acid having 4-12 carbon atoms.

Examples of polyalkylpiperidine compounds from this class are the following compounds: 1) 4-hydroxy-2,2,6,6-tetramethyipiperidine 2) 1-allyl-4-hydroxy-2, 2, 6,6-tetramethylpiperidine 3) 1-benzyl-4-hydroxy-2, 2,6, 6-tetramethylpiperidine 4) 1-(4-tert-butyl-2-butenyl)-4-hydroxy-2,2, 6,6-tetramethylpiperidine 5) 4-stearoyloxy-2, 2, 6,6-tetramethylpiperidine 6) 1-ethyl-4-salicyloyloxy-2, 2,6,6-tetramethylpiperidine 7) 4-methacryloyloxy-1, 2,2,6,6-pentamethylpiperidine 8) 1,2,2,6, 6-pentamethylpiperidin-4-yl ss-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate 9) di(1-benzyl-2, 2,6, 6-tetramethylpiperidin-4-yl) maleate 10) di (2, 2,6, 6-tetramethylpiperidin-4-yl) succinate 11) di (2,2,6,6-tetramethylpiperidin-4-yl) glutarate 12) di (2,2,6, 6-tetramethylpiperidin-4-yl) adipate 13) di (2,2,6, 6-tetramethylpiperidin-4-yl) sebacate 14) di (1,2,2,6, 6-pentamethylpiperidin-4-yl) sebacate 15) di (1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) sebacate 16) di (1-allyi-2, 2,6,6-tetramethyipiperidin-4-yl) phthalate 17) 1-hydroxy-4-ss-cyanoethoxy-2, 2,6,6-tetramethylpiperidine 18) 1-acetyl-2, 2,6,6-tetramethylpiperidin-4-yl acetate 19) tri (2,2,6, 6-tetramethylpiperidin-4-yl) trimellitate 20) 1-acryloyl-4-benzyloxy-2, 2,6, 6-tetramethylpiperidine 21) di (2,2,6,6-tetramethylpiperidin-4-yl) diethylmalonate 22) di (1, 2,2,6,6-pentamethyipiperidin-4-yl) dibutylmalonate 23) di (1, 2,2, 6,6-pentamethylpiperidin-4-yl) butyl (3,5-di-tert-butyl-4-hydroxybenzyi) malonate 24) di (1-octyloxy-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate 25) di (1-cyclohexyloxy-2, 2,6,6-tetramethyipiperidin-4-yl) sebacate 26) hexane-1', 6'-bis (4-carbamoyloxy-1-n-butyl-2, 2,6,6-tetramethylpiperidine) 27) toluene-2', 4'-bis- (4-carbamoyloxy-1-n-propyl-2, 2,6,6-tetramethylpiperidine) 28) dimethylbis (2,2,6,6-tetramethylpiperidin-4-oxy) silane 29) phenyltris (2,2,6,6-tetramethylpiperidin-4-oxy) silane 30) tris (1-propyl-2, 2,6, 6-tetramethylpiperidin-4-yl) phosphite 30-a) tris (1-methyl-2, 2,6,6-tetramethylpiperidin-4-yl) phosphite 31) tris (1-propyl-2, 2, 6, 6-tetramethylpiperidin-4-yl) phosphate 32) phenyl bis (1,2,2,6, 6-pentamethylpiperidin-4-yl) phosphonate 33) 4-hydroxy-1, 2,2,6,6-pentamethylpiperidine 34) 4-hydroxy-N-hydroxyethyl-2, 2,6,6-tetramethylpiperidine 35) 4-hydroxy-N-(2-hydroxypropyl)-2, 2,6,6-tetramethylpiperidine 36) 1-glycidyl-4-hydroxy-2, 2,6,6-tetramethylpiperidine 36-a) 1, 2, 3,4-tetrakis [2, 2,6,6-tetramethylpiperidin-4-yfoxycarbonyl] butane 36-b) 1,2,3, 4-tetrakis[1, 2,2,6,6-pentamethylpiperidin-4-yloxycarbonyi] butane 36-c) 2,2,6,6-tetramethylpiperidin-4-yloxycarbonyl (C, s-C"alkane)

(b') A compound of the formula (lb)

in which n2 is the number 1,2 or 3, G, G, and Gon are as defined under (a'), G, 3 is hydrogen, C,-C, 2alkyl, CZ-Cshydroxyalkyl, Cs-C7cycloaJkyl, CT-C8aralkyl, C1-C18alkanoyl, C3-C5alkenoyl, benzoyl or a group of the formula

and G14, if n2 is 1, is hydrogen, C,-C,salkyl, C3-Cealkenyl, Cs-C7cycloalkyl, C,-C4alkyl which is substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide group, glycidyl, a group of the formula-CH2-CH (OH)-Z or of the formula-CONH-Z, in which Z is hydrogen, methyl or phenyl ; G14, if n2 is 2, is C2-C12alkylene, C6-C12arylene, xylylene, a -CH2-CH(OH)-CH2 group or a -CH2-CH (OH)-CH2-0-D-0- group, in which D is C2-C10alkylene, C6-C15arylene, C6-C12cycloalkylene, or. provided that G13 is not alkanoyl, alkenoyi or benzoyl, G, 4 can aftematively be 1-oxo-C2-C12alkylene, a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or altematively the group-CO-, G,4, if n2 is 3, is a group

or, if n2 is 1, G, 3 and G14 together can be the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

Some examples for the radicals G13, G14 and D are given below.

Any alkyl substituents are as defined above for (a').

Any CS-C7cycloalkyl substituents are, in particular, cyclohexyl.

CTC8aralkyl G, 3 is, in particular, phenylethyl or especially benzyl.

Cz-Cshydroxyalkyl G13 is, in particular, 2-hydroxyethyf or 2-hydroxypropyl.

C1-C16alkanoyl G13 is, for example, formyl, acetyl, propionyl, butyryl, octanoyí, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl, and C3-Csalkenoyl G13 is, in particular, acryloyl.

C2-C8alkenyl G14 is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

G14 as a hydroxyl-, cyano-, alkoxycarbonyl-or carbamide-substituted Ct-C4alkyl can be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)ethyl.

Any C2-Ct2alkylene radicals are, for example, ethylene, propylene, 2, 2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

Any C6-C15arylene substituents are, for example, o-, m-or p-phenylene, 1,4-naphthyfene or 4,4'-diphenylene.

C6-C, 2cycfoalkylene is, in particular, cyclohexyiene.

G, 4 as 1-oxo-C2-C12alkylene is preferably a group

Preference is given to compounds of the formula (lb) in which n2 is 1 or 2, G and G1 are hydrogen, Gn is hydrogen or methyl, G, 3 is hydrogen, C1-C12alkyl or a group of the formula

and G14, in the case where n=1, is hydrogen or Ci-Cnaikyt, and, in the case where n=2, is C2-C8alkylene or 1-oxo-C2-C8alkylene.

Examples of polyalkylpiperidine compounds from this class are the following compounds: 37) N, N'-bis (2,2,6, 6-tetramethylpiperidin-4-yl)hexamethylene-1,8-diamine 38) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1, 6-diacetamide 39) bis (2,2,6,6-tetramethylpiperidin-4-yl) amine 40) 4-benzoylamino-2, 2,6,6-tetramethylpiperidine 41) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl)-N, N'-dibutyladipamide 42) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl)-N, N'-dicyclohexyl-2-hydroxypropylene 1,3-diamine 43) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl)-p-xylylenediamine 44) N, N'-bis (2,2,6,6-tetramethy) pipendin-4-y)) succinamide 45) bis (2,2,6,6-tetramethylpipendin-4-yl) N- (2,2,6,6-tetramethyipiperidin-4-yi)-B aminodipropionate 46) The compound of the formula

47) 4- (bis-2-hydroxyethylamino)-1, 2, 2,6,6-pentamethylpiperidine 48) 4- (3-methyl-4-hydroxy-5-tert-butyl-benzamido)-2, 2, 6, 6-tetramethylpiperidine 49) 4-methacrylamido-1, 2,2,6, 6-pentamethylpiperidine

49-b) N, N', N"-tris [2, 2, 6, 6-tetramethylpiperidin-4-ylamino(2-hydroxypropylene)]isocyanurate 49-c) 2- (2, 2,6, 6-tetramethylpiperidin-4-ylamino)-2-(2, 2,6,6-tetramethylpiperidin-4 ylaminocarbonyi) propane 49-d) 1,6-bis [N- (2,2,6,6-tetramethylpiperidin-4-yl) formylaminolhexane

(c') A compound of the formula (lc)

in which n3 is the number 1 or 2, G, G, and Gon are as defined under (a'), and Gis, if n3 is 1, is C2-C8alkylene, C2-C8hydroxyalkylene or C4-C22acyloxyalkylene, and if n3 is 2, G, s is the (-CH2) 2C (CH2-) 2 group.

C2-Caalkylene or C2-C8hydroxyalkylene G15 is, for example, ethylene, 1-methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene.

C4-C22acyloxyalkylene G15 is, for example, 2-ethyl-2-acetoxymthylpropylene. Examples of polyalkylpiperidine compounds from this class are the following compounds: 50) 9-aza-8,8,10, 10-tetramethyl-1, 5-dioxaspiro [5.5] undecane 51) 9-aza-8,8,10, 10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]undecane 52) 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro [4. 5] decane 53) 9-aza-3-hydroxymethyl-3-ethyl-8, 8,9,10,10-pentamethyl-1, 5-dioxaspiro [5.5] un decane 54) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8, 8, 10,10-tetramethyl-1,5-dioxaspiro[5.5] undecane 55) 2,2,6,6-tetramethylpiperidine-4-spiro-2'- (1', 3'-dioxane)-5'-spiro-5"- (1", 3"-dioxane) 2"-spiro-4"'- (2"', 2", 6"', 6"'-tetramethylpiperidine) (d') A compound of the formula (Id-1), (Id-2) or (ld-3),

in which n4 is the number 1 or 2, G, G, and G"are as defined under (a'), G, 6 is hydrogen, C,-C, Zalkyl, allyi, benzyi, giycidyl or C2-C6alkoxyalkyl, and G, 7, if n4 is 1, is hydrogen, C,-C, zalkyl, C3-Csalkenyl, CrCgaralkyi, C5-C7cycloalkyi, C2-C4hydroxyalkyl, C2-C6alkoxyalkyl, C6-C10aryl, glycidyl or a group of the formula - (CH2) p-COO-Q or-(CH2) p-O-CO-Q, in which p is 1 or 2, and Q is C,-C4alkyl or phenyl, and G17, if n is 2, is C2-C12alkylene, C4-C12alkenylene, C6-C12arylene, a group of the formula -CH2-CH (OH)-CH2-O-D'-O-CH2-CH (OH)-CH2-, in which D'is C2-C10alkylene, C6-C15arylene, C6-C12cycloalkylene or a group of the formula-CH2CH (OD") CH2- (OCH2-CH (OD") CH2) 2-, in which D"is hydrogen, C,-C, ealkyi, allyl, benzyl, C2-C, 2alkanoyl or benzol, T, and T2, independently of one another, are hydrogen, C1-C18alkyl or unsubstituted or halogen-or C,-C4alkyl-substituted C6-C, oaryl or C7-C9aralkyl, or T, and T2 together with the carbon atom bonding them form a CrC, 4cycloalkane ring.

A compound of the formula (ld-3) is preferred.

Some examples of the several variables in the formulae (Id-1), (Id-2) and (ld-3) are given below.

Any C1-C12alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tertbutyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Any C,-C, 8alkyl substituents can be, for example, the abovementioned groups and in addition, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Any C2-C6alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyi or propoxypropyl.

C3-Csalkenyl G17 7 is, for example, 1-propenyl, allyi, methallyl, 2-butenyi or 2-pentenyl.

C7-C9aralkyl G17, T1 and T2 are, in particular, phenethyi or especially benzyl. If T, and T2 together with the carbon atom form a cycloalkane ring, this can be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.

C2-C4hydroxyalkyl Gt7 is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

C6-C, oaryl G", T, and T2 are, in particular, phenyl or a-or P-naphthyl, which are unsubstituted or substituted by halogen or C1-C4alkyl.

C2-C12alkylene G17 is, for example, ethylene, propylene, 2,2-dimethylpropyfene, tetramethylene, hexamethytene, octamethylene, decamethylene or dodecamethylene.

C4-C12alkenylene G17 is, in particular, 2-butenylene, 2-pentenylene or 3-hexenyiene.

C6-C12arylene G17 is, for example, o-, m-or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

C2-C12alkanoyl D"is, for example, propionyl, butyryl, octanoyi, dodecanoyl, but preferably acetyl.

C2-C10alkylene, C6-C15arylene or C6-C, 2cycloalkylene D'have, for example, one of the definitions given for D under (b').

Examples of polyalkylpiperidine compounds from this class are the following compounds: 56) 3-benzyl-1, 3,8-triaza-7,7,9, 9-tetramethylspiro[4.5]decane-2,4-dione 57) 3-n-octyl-1, 3, 8-triaza-7, 7, 9, 9-tetramethylspiro [4. 5] decane-2,4-dione 58) 3-allyl-1, 3,8-triaza-1,7,7,9,9-pentamethylspiro [4. 5] decane-2, 4-dione 59) 3-glycidyl-1, 3,8-triaza-7,7,8,9,9-pentamethylspiro [4.5] decane-2,4-dione 60) 1,3,7,7,8,9, 9-heptamethyl-1, 3,8-triazaspiro [4.5] decane-2,4-dione 61) 2-isopropyl-7, 7,9,9-tetramethyi-1-oxa-3, 8-diaza-4-oxospiro [4. 5] decane 62) 2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro [4.5] decane 63) 2,2,4, 4-tetramethyl-7-oxa-3, 20-diaza-21-oxodispiro [5. 1.11.2] heneicosane 64) 2-but-7, 7,9,9-tetramethyl-1-oxa4,8-diaza-3-oxospiro [4. 5] decane and preferably : 65) 8-acetyl-3-dodecyl-1, 3,8-triaza-7,7,9,9-tetramethylspiro [4.5] decane-2,4-dione and the compounds of the following formulae :

69-b) Mixture of 60 % by weight of and 40 % by weight of

(e') A compound of the formula (le)

in which n5 is the number 1 or 2, and G, 8 is a group of the formula

in which G and G"are as defined under (a'), and G, and G2 are hydrogen, methyl or, together, are a substituent =O, E is-O-or-ND"'-, A is C2-C6alkylene or -(CH2)3-O- and x, is the number 0 or 1, D"'is hydrogen, C,-Cl2alkyl, C2-Cshydroxyalkyi or C5-C7cycloalkyl, G19 is identical to G, e or is one of the groups-N (G2,) (G22),-OG23,-N (H) (CH2OG23) or -N (CH20G23) 2, G20, if n = 1, is identical to G, 8 or Gig and, if n = 2, is an-E-DN-E-group, in which DN is C2-C8alkylene or C2-C8alkylene which is interrupted by 1 or 2-NG2,-groups, G2, is C1-C12alkyl, cyclohexyl, benzyl or C,-C4-hydroxyalkyl or a group of the formula

G22 is C,-C, 2alkyl, cyclohexyl, benzyl or C,-C4hydroxyalkyl, and G23 is hydrogen, C1-C12alkyl or phenyl, or G2, and G22 together are C4-Csalkylene or C4-Csoxaalkyiene, for example-CH2CH2-O-CH2CH2-, or a group of the formula -CH2CH2-N(G11)-CH2CH2-.

Some examples of the several variables in the formula (le) are given below.

Any C1-C12alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyi, tertbutyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Any hydroxyalkyl substituents are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

Any C5-C7cycloalkyl substituents are, for example, cyclopentyl, cyclohexyl or cycloheptyl.

Cyclohexyl is preferred.

C2-C6alkylene A is, for example, ethylene, propylene, 2, 2-dimethylpropylene, tetramethylene or hexamethylene.

If Gz, and G22 together are C4-Csalkylene or oxaalkylene, they are, for example, tetramethy lene, pentamethylene or 3-oxapentamethylene.

Examples of polyalkylpiperidine compounds from this class are the compounds of the following formulae :

where R has the same meaning as in compound 74.

where R'has the same meaning as in compound 76.

(f') A compound of the formula (If)

wherein Gn is as defined under (a').

A preferred example from this ciass is the following compound:

(g') Oligomeric or polymeric compounds whose recurring structural unit contains a 2,2,6,6 tetraalkylpiperidinyl radical, in particular polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly (meth) acrylates, poly (meth) acry) amides and copolymers thereof which contain such radical.

Examples of 2,2,6,6-polyalkylpiperidine compounds from this class are the compounds of the following formulae, where m, to M14 ils a number from 2 to about 200, preferably 2 to 100, for example 2 to 50, 2 to 40 or 3 to 40 or 4 to 10.

The meanings of the end groups which saturate the free valences in the oligomeric or polymeric compounds listed below depend on the processes used for the preparation of said compounds. The end groups can also in addition be modified after the synthesis of the compounds.

In the compounds 81 and 82, the end group bonded to the-O-can be, for example, hydrogen or a group-CO- (CH2) 2-COO-Y or-CO- (CH2) 4-COO-Y, respectively, with Y being hydrogen or C1-C4alkyl and the end group bonded to the diacyl can be, for example,-O-Y or a group

In the compound 83, the end group bonded to the amino residue can be, for example, a group

and the end group bonded to the diacyl residue can be, for example, Cl.

In the compounds 84-1 and 84-2, the end group bonded to the triazine residue can be, for example, chlorine or a group

and the end group bonded to the diamino group can be, for example, hydrogen or a group

It may be convenient to replace the chlorine attached to the triazine by e. g.-OH or an amino group. Suitable amino groups are typically : pyrrolidin-1-yf, morpholino,-NH2,-N (C,-Cealkyl) 2 and -NY' (Ci-Csa) kyf) wherein Y'is hydrogen or a group of the formula

In the compound 85, the end group bonded to the 2,2,6,6-tetramethylpiperidin-4-ylamino residue can be, for example, hydrogen and the end group bonded to the 2-hydroxypropylene residue can be, for example,

In the compound 86, the end group bonded to the-O-can be, for example, hydrogen or

and the end group bonded to the diacyl residue can be, for example,-OCH3 or Cl.

In the compound 87, the end group bonded to the-O-can be, for example, hydrogen or

1 and the end group bonded to the diacyl radical can be, for example,-OCH3 or Cl.

In the compound 88, the end group bonded to the-O-can be, for example, hydrogen or

and the end group bonded to the diacyS radical can be, for example,-OCH3 or Cl.

In the compound 89, the end group bonded to the-CH2-can be, for example, hydrogen and the end group bonded to the ester residue can be, for example,

In the compound 90, the end group bonded to the-CH2-can be, for example, hydrogen and the end group bonded to the ester residue can be, for example,

In the compound 91, the end group bonded to the-CH2-can be, for example, hydrogen and the end group bonded to the amide residue can be, for example,

In the compound 92, the end group bonded to the triazine residue can be, for example, chlorine or a group

and the end group bonded to the diamino residue can be, for example, hydrogen or a group

It may be convenient to replace the chlorine attached to the triazine by e. g.-OH or an amino group. Suitable amino groups are typically : pyrrolidin-1-yl, morpholino,-NH2,-N (C,-C8alkyf) 2 and-NY' (C,-C8alkyl) wherein Y'is hydrogen or a group of the formula

Preferred is also a compound which corresponds to compound 92 wherein the 2,2,6,6 tetramethylXpiperidyl groups are replace by 1,2,2,6,6-pentamethyl-4-piperidyl groups.

In the compound 93, the end group bonded to the diamino residue can be, for example, hydrogen and the end group bonded to the-CH2CH2-residue can be, for example,

In the compound 94, the end group bonded to the diamino residue can be, for example, hydrogen and the end group bonded to the diacyl residue can be, for example, Ci.

in which R"is a group of the formula

or the chain branching

R"'is a group of the formula (95-1), and m', 5 and m", 5 are each a number from 0 to 200, preferably 0 to 100, in particular 0 to 50, with the proviso that m't5 + m"15 is a number from 2 to 200, preferably 2 to 100, in particular 2 to 50. In the compound 95, the end group bonded to the diamino residue can be, for example, hydrogen and the end group bonded to the-CH2CH2-group can be, for example, halogen, in particular Cl or Br.

Further examples for polymeric compounds are : 1) A compound of the formula (96-I) or (96-li)

wherein ml6 and m, 6* are a number from 2 to 50.

During the preparation, the compounds of the formulae (96- !) and (96-li) can be obtained together as a mixture and therefore, can also be employed as such. The (96-1) : (96-lu) weight ratio is, for example, from 20: 1 to 1: 20 or from 1: 10 to 10: 1.

In the compounds of the formula (96-f), the terminal group bonded to the nitrogen can be, for example, hydrogen and the terminal group bonded to the 2-hydroxypropylene radical can be, for example, a

group.

In the compounds of the formula (96-il), the terminal group bonded to the dimethylene radical can be, for example,-OH, and the terminal group bonded to the oxygen can be, for example, hydrogen. The terminal groups can also be polyether radical.

2) A compound of the formula (97)

wherein G24, G25, G26, G27 and G28, independently of one another, are a direct bond or C1-C10alkylene, G11 is as defined under (a') and M17 is a number from 1 to 50.

In the compound of the formula (97), the end group bonded to the > C=O group can be, for example,

and the end group bonded to the oxygen can be, for example

Preferred are the following two compounds:

wherein the mean value of m17 is 2.5.

3) A compound of the formula (98)

in which approximately one third of the radicals RN are-C2H5 and the others are a group

and m, 8 is a number in the range from 2 to 200, preferably 2 to 100, in particular 2 to 50.

In the compound (98), the end group bonded to the-CH2-residue can be, for example, hydrogen and the end group bonded to the-CH (C02RN)- residue can be, for example, -CH=CH-COOR'V.

4) A compound of the formula (99)

in which G11 is as defined under (a'), G29 and G32, independently of one another, are a direct bond or a-N (X,)-CO-XrCO-N (X3)-group, where X, and X3, independently of one another, are hydrogen, C1-C9alkyl, CfC, 2cycloalkyl, phenyl, CrCgphenylalkyl or a group of the formula (99-1)

and X2 is a direct bond or C1-C4alkylene, G30, G31, G34 and G35, independently of one another, are hydrogen, C1-C30alkyl, C5-C1 2cycloalkyl or phenyl, G33 is hydrogen, C,-C30alkyl, Cs-C, 2cycloalkyl, C,-Cgphenylalkyl, phenyl or a group of the formula (99-1), and m19 is a number from 1 to 50.

In the compounds of the formula (99), the end group bonded to the 2,5-dioxopyrrolidine ring can be, for example, hydrogen, and the end group bonded to the-C (G34) (G35)- radical can be, for example,

Examples of the compounds of the formula (99) are:

wherein GI, is hydrogen or methyl, and m19 is a number from 1 to 25.

5) A product obtainable by reacting an intermediate product, obtained by reaction of a polyamine of the formula (100a) with cyanuric chloride, with a compound of the formula (100b) H2N-(CH2)m'-NH-(CH2)m"-NH-(CH2)m"'-NH2 (100a) 20 20 in

in which m'zo, m"2o and m"'20, independently of one another, are a number from 2 to 12, G36 is hydrogen, C,-C, 2alkyl, CS-Cl Zcycloalkyl, phenyl or C7-Cgphenylalkyl, and G11 is as defined under (a'). A preferred product has the Chemical Abstracts-CAS No.

136 504-96-6 (Compound 100-A). in general, the above reaction product can be represented for example by a compound of the formula 100-1,100-2 or 100-3. It can also be in the form of a mixture of these three compounds.

A preferred meaning of the formula (100-1) is

A preferred meaning of the formula (100-2) is

A preferred meaning of the formula (100-3) is

In the above formulae 100-1 to 100-3, m2o is preferably 1 to 20.

6) A compound of the formula (101)

in which Guis as defined under (a'), G37 is C,-C, oalkyl, C5-C, 2cycloalkyl, C,-C4alkyl- substituted C5-C12cycloalkyl, phenyl or C,-C, oaikyl-substituted phenyi, G38 is C3-C Oalkylene and m21 is a number from 1 to 50.

In the compounds of the formula (101), the terminal group bonded to the silicon atom can be, for example, (G37) 3Si-O-, and the terminal group bonded to the oxygen can be, for example,-Si (G37) 3.

The compounds of the formula (101) can also be in the form of cyclic compounds if m2, is a number from 3 to 10, i. e. the free valences shown in the structural formula then form a direct bond.

An example of a compound of the formula (101) is

with m21 being a number from 1 to 20.

In the above shown oligomeric and potymenc compounds, examples of alkyl are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2 ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, nheptyl, isoheptyl, 1, 1, 3, 3-tetramethylbutyf, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethyl- hexyl, 1,1,3-trimethylhexyl, 1,1,3, 3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethyihexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl and docosyl ; examples of cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl ; an example of CTCgphenylalkyl is benzyl ; and examples of alkylene are ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2, 2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethytene.

(h') A compound of the formula (lh)

in which n6 is the number 1 or 2, G and Gare as defined under (a'), and G14 is as defined under (b'), but G, 4 cannot be-CONH-Z and-CH2-CH (OH)-CH2-O-D-O-.

Examples of such compounds are the following :

(i') A compound of the formula (li)

wherein the radicals G39, independently of one another, are a group of the formula (li-1)

in which G44 is C,-C, 2alkyl or C5-C12cycloalkyl, G41 is C2-C, 2alkylene and G42 is hydrogen, C1-C8alkyl, -O-, -CH2CN, C3-C6alkenyl, C7-C9phenylalkyl, C7-C9phenylalkyl which is substituted on the phenyf radical by C,-C4alkyl ; or C,-C8acyl.

Alkyl is for example C,-C4alkyl, in particular methyl, ethyl, propyl or butyl.

Cycloalkyl is preferably cyclohexyl.

Alkylene is for example ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene or hexamathylene.

Alkenyl is preferably allyt.

Phenylalkyl is preferably benzyl.

Acyl is preferably acetyl.

Examples of compounds from this class are the compounds of the following formulae :

The sterically hindered amine compound (component (A)) is preferably one of the above compounds 1 to 106. The compounds 5,10,13,14,24,25,36-a, 36-b, 36-d, 49-a-I, 49-e, 63,75,76,80-a, 81,84-1,84-2,92,93,96-I, 96-II, 97-I, 97-II, 99-I, 100-A, 101-I, 105 and 106 are of interest. The compounds 13,14,36-a, 36-b, 36-d, 76,81, 84-1, 96-I, 96-II, 100-A, 101-I, 105 and 106 are preferred. The compounds 13, 14,36-d, 81,84-1,96-l, 96-vil, 100-A, 101-1, 105 and 106 are particularly preferred.

Examples of an organic salt of Ca are Ca-stearate, Ca-laurate, Ca-lactate and Ca-stearoyl- lactate.

Examples of an inorganic salt of Ca are CaO and Ca (OH) 2.

The organic salt of zinc or magnesium defined in component (C) is preferably a compound of the formula MeL2 in which Me is zinc or magnesium and L is an anion of an organic acid or of an enol. The organic acid can, for example, be a suffonic acid. suffinic add, phosphonic acid or phosphinic acid, but is preferably a carboxyiic acid. The acid can be aliphatic, aromatic, araliphatic or cycloaliphatic ; it can be linear or branched; it can be substituted by hydroxyl or alkoxy groups; it can be saturated or unsaturated and it preferably contains 1 to 24 carbon atoms.

Examples of carboxylic acids of this type are formic, acetic, propionic, butyric, isobutyric, caprioic, 2-ethylcaproic, caprylic, capric, lauric, palmitic, stearic, behenic, oleic, lactic, ricinoleic, 2-ethoxypropionic, benzoic, salicylic, 4-butyfbenzoic, toluic, 4-dodecyibenzoic, phenylacetic, naphthylacetic, cyclohexanecarboxylic, 4-butyicyciohexanecarboxylic or cyclohexylacetic acid. The carboxytic acid can also be a technical mixture of carboxylic acids, for example technical mixtures of fatty acids or mixtures of alkylated benzoic acids.

Examples of organic acids containing sulfur or phosphorus are methanesulfonic, ethanesulfonic, a, a-dimethylethanesulfonic, n-butanesulfonic, n-dodecanesulfonic, benzenesulfonic, toluenesulfonic, 4-nonyibenzenesulfonic, 4-dodecylbenzenesulfonic or cyclohexanesulfonic acid, dodecanesulfinic, benzenesulfinic or naphthalenesulfinic acid, butylphosphonic acid, phenylphosphonic acid, monomethyl or monoethyl phenylphosphonate, monobutyl benzylphosphonate, dibutylphosphinic acid or diphenylphosphinic acid.

If L is an enolate anion, it is preferably an anion of a p-dicarbony) compound or of an o-acylphenol. Examples of p-dicarbony) compounds are acetylacetone, benzoylacetone, dibenzoylmethane, ethyi acetoacetate, butyl acetoacetate, lauryl acetoacetate or a-acetyicyclohexanone. Examples of o-acylphenols are 2-acetylphenol, 2-butyroylphenol, 2-acetyl-1-naphthol, 2-benzoylphenol or salicylaldehyde. The enolate is preferably the anion of a 3kicarbonyl compound having 5 to 20 carbon atoms.

Organic salts of zinc or magnesium are preferably an acetylacetonate or an aliphatic monocarboxylate having, for example, 1 to 24 carbon atoms. Magnesium acetate, laurate and stearate, zinc formate, acetate, oenanthate, laurate and stearate as well as zinc acetyiacetonate and magnesium acetylacetonate are some of the particular preferred examples.

Zinc stearate, magnesium stearate, zinc laurate, magnesium laurate, zinc acetylacetonate, magnesium acetylacetonate, zinc acetate and magnesium acetate are of special interest.

The inorganic salt of zinc or magnesium is for example zinc oxide, magnesium oxide, zinc hydroxide, magnesium hydroxide, or a carbonate containing compound such as # Zn-hydroxide-carbonate, Mg-hydroxide-carbonate, dolomite, e. g a Ca/Mg carbonate such as sMicrodol Super from eMicro Minerals ; or a natural or synthetic hydrotalcite.

The natural hydrotalcite is held to possess a structure Mg6Al2(OH)16CO3 # 4H2O.

A typical empirical formula of a synthetic hydrotalcite is Al2Mg4.35OH11.36CO3(1.67) # xH2O.

Examples of the synthetic product include : Mgo. 7Al0. 3 (OH) 2 (CO3) 0., 5 # 0. 54 H20, Mg4.5Al2(OH)13CO3 # 3.5H2O, or Mg4. 2Al (OH), 12. 4C03.

Preferred synthetic hydrotalcites are L-55R#II from sREHEIS as well as sZHT4A and #DHT-4A from sKyowa Chemical Industry Co.

A preferred embodiment of this invention relates to a stabilizer mixture wherein component (C) is hydrotalcite, dolomite, Zn-hydroxide-carbonate, Mg-hydroxide-carbonate, Zn-oxide, Mg-oxide, Zn-hydroxide, Mg-hydroxide, Zn-stearate, Mg-stearate, Zn-laurate, Mg-laurate, Zn-acetylacetonate, Mg-acetylacetonate, Zn-acetate or Mg-acetate.

The following combinations of components (B) and (C) are particu) any preferred: # Ca oxide and Mg stearate Ca oxide and Zn stearate Ca oxide and hydrotalcite (#DHT-4A) Ca hydroxide and Mg stearate Ca hydroxide and Zn stearate A further preferred embodiment of this invention relates to a stabilizer mixture containing additionally (D1) a pigment or (D2) an UV absorber or (D3) a pigment and an UV absorber.

The pigment (component (D1)) may be an inorganic or organic pigment.

Examples of inorganic pigments are titanium dioxide, zinc oxide, carbon black, cadmium sulfide, cadmium selenide, chromium oxide, iron oxide, lead oxide and so on.

Examples of organic pigments are azo pigments, anthraquinones, phthalocyanines, tetrachloroisoindolinones, quinacridones, isoindolines, perylenes, pyrrolopyrroles (such as Pigment Red 254) and so on.

All pigments described in"Gachter/Muller : Plastics Additives Handbook, 3rd Edition, Hanser Publishers, Munich Vienna New York", page 647 to 659, point 11.2.1.1 to 11.2.4.2 can be used as component (D1).

A particularly preferred pigment is titanium dioxide, optionally in combination with an organic pigment.

Examples of such organic pigments are: C. I. (Colour Index) Pigment Yellow 93, C. I. Pigment Yellow 95, C. I. Pigment Yellow 138, C. I.

Pigment Yellow 139, C. l. Pigment Yellow 155, C. I. Pigment Yellow 162, C. I. Pigment Yellow 168, C. l. Pigment Yellow 180, C. I. Pigment Yellow 183, C. I. Pigment Red 44, C. I. Pigment Red 170, C. I. Pigment Red 202, C. l. Pigment Red 214, C. I. Pigment Red 254, C. I. Pigment Red 264, C. I. Pigment Red 272, C. I. Pigment Red 48: 2, C. I. Pigment Red 48: 3, C. I. Pigment Red 53: 1, C. I. Pigment Red 57: 1, C. i. Pigment Green 7, C. l. Pigment Blue 15: 1, C. I.

Pigment Blue 15: 3 and C. I. Pigment Violet 19.

Examples of the UV absorber (component (D2)) are a 2- (2'-hydroxyphenyl) benzotriazole, a 2-hydroxybenzophenone, an ester of substituted or unsubstituted benzoic acid, an acryiate, an oxamide, a 2- (2-hydroxyphenyl)-1, 3,5-triazine, a monobenzoate of resorcinol or a formamidine.

The 2- (2'-hydroxyphenyl) benzotriazole is e. g. 2- (2'-hydroxy-5'-methyiphenyl)-benzotriazole, 2- (3', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzo triazole, 2- (2'-hydroxy-5'- (1, 1,3, 3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl 2'-hydroxyphenyi)-5-chloro-benzotriazole, 2- (3'-tert-butyi- 2'-hydroxy-5'-methylphenyl)-5- chloro-benzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'- hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3', 5'-di-tert-amyi-2'-hydroxyphenyl) benzotriazole, 2- (3', 5'-bis- (a, a-dimethylbenzyl)-2'-hydroxyphenyl) benzotriazole, mixture of 2- (3'-tert-butyl-2'- hydroxy-5'- (2-octyloxycarbonylethyl) phenyl)-5-chloro-benzotriazole, 2- 3'-tert-butyl-5'- [2- (2- ethylhexyioxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2- (3'-tert-butyl-2'- hydroxy-5'- (2-methoxycarbonylethyl) phenyl)-5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-- hydroxy-5'- (2-methoxycarbonylethyl) phenyl) benzotriazofe, 2- (3'-tert-butyl-2'-hydroxy-5'- (2- octyloxycarbonylethyl) phenyi) benzotriazole, 2- (3'-tert-butyl-5'- [2- (2-ethyihexyloxy) carbonyl- ethyl]-2'-hydroxyphenyi benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotri- azole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2' methylene-bis [4-(1, 1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol] or the transesterification product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300 ; [R-CH2CH2-COO (CH2) 3l2 where R = 3'-tert-butyl-4' hydroxy-5'-2H-benzotriazol-2-ylphenyl.

2- (3', 5'-Di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- methyfphenyi)-5-chloro-benzotriazole and 2- (3', 5'-di-tert-amyl-2'-hydroxyphenyl)- benzotriazole are preferred.

The 2-hydroxybenzophenone is for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2', 4'-trihydroxy or 2'-hydroxy-4, 4'-dimethoxy derivatives.

2-Hydroxy-4-octyloxybenzophenone is preferred.

The ester of a substituted or unsubstituted benzoic acid is for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylben- zoyl) resorcinol, benzoyl resorcinol, 2,4-di-tertbutyfphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate or 2-methyl-4, 6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2, 4-Di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl-4hydroxybenzoate are preferred.

The acrylate is for example ethyl &alpha;-cyano-ss,ss-diphenylacrylate, isooctyl &alpha;-cyano-ss,ss-di- phenylacrylate, methyl a-carbomethoxycinnamate, methyl &alpha;-cyano-ss-methyl-p-methoxy- cinnamate, butyl a-cyano-p-methyl-p-methoxy-cinnamate, methyl a-carbomethoxy-pmethoxycinnamate or N- (j3-carbomethoxy-p-cyanovinyl)-2-methylindoline.

The oxamide is for example 4,4'-diocyoxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyioxy5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5, 5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyfoxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyi-2'-ethoxanilide or its mixture with 2-ethoxy-2'-ethyl-5, 4'-di-tert-butoxanilide or mixtures of ortho-and para-methoxydisubstituted oxanilides or mixtures of o-and p-ethoxy-disubstituted oxanilides.

The 2- (2-hydroxyphenyl)-1, 3,5-triazine is for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyi)- 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-dimethylphenyi)-1, 3,5-triazine, 2,4-bis (2-hydroxy-4-propyl- oxyphenyl)-6-(2, 4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis (4methylphenyl)-1, 3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4, 6-bis (2,4-dimethylphenyl)1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis (2, 4-dimethylphenyl)-1, 3,5-triazine, 2 [2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4, 6-bis (2, 4-dimethyl)-1, 3, 5-triazine, 2-[2 hydroxy-4- (2-hydroxy-3-octyloxy-propytoxy) phenyl]-4, 6-bis (2, 4-dimethyl)-1, 3,5-triazine, 2- [4 (dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4, 6-bis (2, 4-dimethylphenyl)-1,3,5-triazine, 2- (2-hydroxy-4- (2-hydroxy-3-dodecyloxy-propoxy) phenyl]-4, 6-bis (2,4-dimethyl phenyl)-1, 3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1, 3,5-triazine, 2- (2hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2, 4,6-tris [2-hydroxy-4- (3-butoxy-2- hydroxy-propoxy) phenyl]-1, 3,5-triazine or 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

2- (2-Hydroxy-4-octyloxyphenyl)-4, 6-bis (2,4-dimethylphenyl)-1,3,5-triazine and 2- (2-hydroxy- 4-hexyloxy) phenyl-4, 6-diphenyl-1, 3,5-triazine are preferred.

The monobenzoate of resorcinol is for example the compound of the formula

The formamidine is for example the compound of the formula

The UV absorber is in particular a 2- (2'-hydroxyphenyl) benzotriazole, a 2-hydroxybenzophenone or a hydroxyphenyltriazine.

The stabilizer mixture according to the present invention is useful for stabilizing polyolefins against degradation induced by light, heat or oxidation. Examples of suitable polyolefins are shown in the following.

1. Polymers of monoolefins and diolefins, for example polypropyiene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbomene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethyiene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethy lene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).

Polyolefins, i. e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following,methods: a) radical polymerisation (normally under high pressure and at elevated temperature). b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or Vlil of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyis and/or aryles that may be either n-or a-coordinated.

These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the poiymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, Ila and/or Illa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylenelhexene copo lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethyiene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethy lene/alkyl acrylate copolymers, ethylene/aikyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene ; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propyl ene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrytic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alter nating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

The invention therefore also relates to a composition containing a polyolefin and the stabilizer mixture as described herein and to a method for stabilizing a polyolefin against degradation induced by light, heat or oxidation, which comprises incorporating into the polyolefin the stabilizer mixture.

The polyolefins listed above under point 1 are preferred. Polyethylene and polypropylene as well as a polyethylene copolymer or a polypropylene copolymer are particularly preferred.

The invention furthermore relates to a composition comprising a polyolefin and a stabilizer mixture containing (A) a sterically hindered amine compound selected from the group consisting of the compounds 13, 14,36-a, 36-b, 36-d, 96-1, 96-li, 100-A, 101-1, 105 and 106 as defined above; (B) an organic salt of Ca, in particular Ca-stearate, or an inorganic salt of Ca; and (C) an organic salt of Mg, an inorganic salt of Mg, an organic salt of Zn or an inorganic salt of Zn ; with the proviso that the polyolefin is polypropylene, when component (A) of the stabilizer mixture is the compound 96-I, 96-li or 100-A.

The components (A), (B), (C) and optionally (D1) and/or (D2) may be added to the polyolefin either individually or mixed with one another.

The sterically hindered amine compound (component (A)) is present in the polyolefin in an amount of preferably 0.01 to 5 %, in particular 0.01 to 1 % or 0.05 to 1 %, relative to the weight of the polyolefin.

The organic or inorganic salt of Ca (component (B)) is present in the polyolefin in an amount of preferably 0.005 to 5 %, in particular 0.02 to 0.5 %, relative to the weight of the polyolefin.

The organic or inorganic salt of Zn or Mg (component (C)) is present in the polyolefin in an amount of preferably 0.01 to 5 %, in particular 0.05 to 0.5 %, relative to the weight of the polyolefin.

The pigment (component (D1)) is optionally present in the polyolefin in an amount of preferably 0.01 to 10 %, in particular 0.05 to 1 %, relative to the weight of the polyolefin.

The UV absorber (component (D2)) is optionally present in the polyolefin in an amount of preferably 0.01 to 1 %, in particular 0.05 to 0.5 %, relative to the weight of the polyolefin.

The total amount of component (D3) (the pigment in combination with the UV absorber) is preferably 0.01 to 10 %, relative to the weight of the organic material. The weight ratio of the UV absorber to the pigment is for example 2: 1 to 1: 10.

When the pigment used is titanium dioxide in combination with an organic pigment as described above, titanium dioxide is preferably present in the organic material in an amount of 0.01 to 5 %, relative to the weight of the organic material, and the organic pigment may be present in an amount of, for example, 0.01 to 2 %, relative to the weight of the organic material.

The weight ratio of the components (A): (B) is preferably 20: 1 to 1: 5.

The weight ratio of the components (A): (C) is preferably 20: 1 to 1: 5.

The weight ratio of the components (A): (D1) is preferably 10: 1 to 1 : 10.

The weight ratio of the components (A): (D2) is preferably 20: 1 to 1: 2.

The weight ratio of the components (A): (D3) is preferably 10: 1 to 1: 10.

The above components can be incorporated into the polyolefin by known methods, for example before or during shaping or by applying the dissolved or dispersed compounds to the polyolefin, if necessary with subsequent evaporation of the solvent. The components can be added to the polyolefin in the form of a powder, granules or a masterbatch, which contains these components in, for example, a concentration of from 2.5 to 25% by weight.

If desired, the components (A), (8), (C) and optionally (D1 and/or (D2) can be melt blended with each other before incorporation in the polyolefin. They can be added to the polyolefin before or during the polymerization or before the crosslinking.

The polyolefin stabilized according to this invention can be used in a wide variety of forms, for example as films, fibres, tapes, moulding compositions, profiles or as binders for paints, adhesives or putties.

The stabilized polyolefin may additionally also contain various conventional additives, for example: 1. Antioxidants 1. 1. Alkylated monoohenots. for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-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-isobutyfphenol, 2, 6-dicyclopentyl-4-methylphenol, 2- (a- methyicyclohexyl)-4, 6-dimethylphenol, 2, 6-dioctadecyi-4-methylphenol, 2,4, 6-tri cyclohexyiphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2, 4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyl heptadec-l'-yi) phenol, 2, 4-dimethyl-6- (l'-methyltridec-l'-yf) phenol and mixtures thereof.

1.2. Alkvithiomethviphenols, for example 2,4-dioctylthiomethyl-6-tert-butyiphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyi-4 methoxyphenol, 2, 5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2, 6 diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2, 5-di-tert-butyl-4hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxy pheny) stearate, bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, for example a-tocopherol, -tocopherol, &gamma;-tocopherol, 8- tocopherol and mixtures thereof (Vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis (6-tert-butyl-4methylphenol), 2,2'-thiobis (4-octyiphenol), 4,4'-thiobis (6-tert-butyl-3-methyfphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4-thiobis- (3, 6-di-sec-amylphenol), 4,4' bis- (2, 6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkviidenebisphenols, for example 2,2'-methylenebis (6-tert-butyi-4methylphenol), 2, 2'-methylenebis(6-tert-butyl-4-ethylphenol), 2, 2'-methylenebis[4 methyl-6- (a-methylcycfohexyl) phenol], 2, 2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methyienebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tertbutylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tertbutyl-4-isobutylphenol), 2,2'-methylenebis [6- (a-methylbenzyl)-4-nonylphenol], 2,2' methylenebis [6- (a, a-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis (2,6-di-tert butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4hydroxy-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-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis [3, 3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5- methyl-phenyl) 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-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra- (5-tert- butyl-4-hydroxy2-methyl phenyl) pentane.

1.7. O-. N-and S-benzvl compounds, for example 3, 5,3', 5'-tetra-tert-butyl-4, 4' dihydroxydibenzyl ether, octadecyl-4-hydroxy-3, 5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4 hydroxybenzyl) amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis (3,5-di-tert-butyi-4-hydroxybenzyf) sulfide, isooctyl-3, 5di-tert-butyl-4- hydroxybenzylmercaptoacetate.

1.8. Hvdroxvbenzvlated malonates, for example dioctadecyl-2, 2-bis- (3, 5-di-tert- butyl-2-hydroxybenzyl)-malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-- methylbenzyl)-malonate, di-dodecylmercaptoethyl-2, 2-bis- (3, 5-di-tert-butyl-4- hydroxybenzyl) malonate, bis [4- (1, 1,3,3-tetramethylbutyf) phenyl]-2,2-bis (3,5-di-tertbutyl-4-hydroxybenzyl) malonate.

1.9. Aromatic hvdroxvbenzyl compounds, 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-4hydroxybenzyl)-2, 3,5,6-tetramethylbenzene, 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-4hydroxyphenoxy)-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, 1,3,5tris (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-t, 3,5-triazine, 1, 3, 5-tris (3,5-dicyclohexyi-4hydroxybenzyl)isocyanurate.

1. 11. Benzylphosphonates, for example dimethyl-2, 5-di-tert-butyi-4-hydroxybenzyl- phosphonate, diethyl-3, 5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy3methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tertbutyl-4-hydroxybenzylphosphonic acid.

1. 12. Acyfaminophenols, for example 4-hydroxyRauranilide, 4-hydroxystearanilide, octyl N- (3, 5-di-tert-butyl-4-hydroxyphenyl) carbamate.

1. 13. Esters of -(3,5-di-tert-butyl-4-hydroxyphenyl)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, triethyfene glycol, pentaerythritol, tris- (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyi-1- phospha-2, 6,7-trioxabicyclo [2.2.2] octane.

1.14. Esters of -(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monoor polyhydric alcools, 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 (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3 thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4- hydroxymethyl-1-phospha-2, 6,7-trioxabicyclo [2.2.2] octane.

1. 15. Esters of -(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono-or polyhydric alcools, 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 (hydroxyethyf) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3 thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1- phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.16. Esters of 3. 5-di-tert-butvl-4-hvdroxvphenvl acetic acid with mono-or polyhydric alcools, e. g. with methanol, ethanol, octanol, octadecanol, 1,6hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3 thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1- phospha-2,6,7-trioxabicyclo [2. 2.2] octane.

1.17. Amides of -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e. g. 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-hydroxyphenylpropionyi) hydrazine.

1.18. Ascorbic acid (vitamin C) 1.19. Aminic antioxidants, for example N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis(1,4-dimethylpentyl)-pphenylenediamine, N, N'-bis (1-ethyi-3-methyipentyl)-p-phenyienediamine, N, N'bis (1-methylheptyl)-p-phenyienediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyi-p-phenyfenediamine, N, N'-bis (2-naphthyl)-p-phenylenediamine, N isopropyl-N'-phenyi-p-phenylenediamine, N- (1, 3-dimethylbutyl)-N'-phenyl-p- phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, Ncyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine.

N, N'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyidiphe- nylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert- octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-di-tert-octyfdiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylamino-phenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethyl aminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyimethane, N, N, N', N'-tetramethyl-4, 4'-diaminodiphenyimethane, 1,2-bis [ (2- methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, Bis [4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono-and dialkylated tert-butyUtert-octyldiphenylamines, a mixture of mono-and dialkylated nonyldiphenylamines, a mixture of mono-and dialkylated dodecyidiphenylamines, a mixture of mono-and dialkylated isopropyVisohexyfdi- phenylamines, a mixture of mono-und dialkylated tert-butyidiphenylamines, 2,3-di hydro-3, 3-dimethyl-4H-1, 4-benzothiazine, phenothiazine, a mixture of mono-und dialkylated tert-butyl/tert-octylphenothiazines, a mixture of mono-un dialkylated tert-octyl-phenothiazines, N-allylphenothiazin, N, N, N', N'-tetraphenyl-1, 4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethyl-piperid-4-yi-hexamethyienediamine, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one.

2,2,6,6-tetramethyipiperidin-4-ol.

2. UV absorbers and light stabifisers Nickei compounds, for example nickel complexes of 2, 2'-thio-bis-[4-(1, 1,3,3-tetramethylbutyl) phenol], such as the 1: 1 or 1: 2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyfdiethanolamine, nickel dibutyidithiocarbamate, nickel salts of the monoalkyl esters, e. g. the methyl or ethyl ester, of 4-hydroxy-3, 5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e. g. of 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.

3. Metal deactivators, for example N, N'-diphenyloxamide, N-salicylal-N'-sallcyloyl hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2, 4-triazole, bis (benzylidene)- oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N, N'-diacetyladipoyl dihydrazide, N, N'-bis (salicyloyl) oxalyl dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tertbutylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-ditert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis (2,4,6-tris (tertbutylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4di-tert-butylphenyl) 4, 4'-biphenylene diphosphonite, 6-isooctyloxy-2, 4,8,10-tetra tert-butyi-12H-dibenz [d, g]-1, 3,2-dioxaphosphocin, 6-fluoro-2, 4, 8,10-tetra-tert-butyl12-methyl-dibenz [d, g]-1,3,2-dioxaphosphocin, bis (2, 4-di-tert-butyl-6-methyl phenyl) methylphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyiphosphite.

5. Hydroxylamines, for example, N, N-dibenzylhydroxyiamine. N, N-diethylhydroxyl- amine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecyihy- droxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, Nhexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated tallow amine.

6. Nitrones, for example, N-benzyt-aipha-phenyl-nitrone, N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl- alpha-tridecyl-nitrone, N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha- heptadecyl-nitrone, N-hexadecyl-alpha-heptadecyl-nitrone, N-ocatadecyl-alpha pentadecyl-nitrone, N-heptadecyi-alpha-heptadecyl-nitrone, N-octadecyl-alpha- hexadecyl-nitrone, nitrone derived from N, N-dialkylhydroxylamine derived from hydrogenated tallow amine.

7. Thiosynergists, for example, dilauryi thiodipropionate or distearyi thiodipro- pionate.

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-mercaptobenzimidazole, zinc dibutyidithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (P-dodecylmercapto) propionate.

9. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyi 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 tin pyrocatecholate.

10. Nudeating agents, for exampie, 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 monoor 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").

11. Fillérs and reinforcino agents, 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.

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

13. Benzofuranones and indolinones for example those disclosed in US-A4325863, US-A-4338244, US-A-5175312, US-A-5216052, US-A-5252643, DE-A4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102 or 3 [4- (2-acetoxyethoxy) phenyl]-5, 7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3 [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2hydroxyethoxy] phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyi) ben zofuran-2-one, 3- (4-acetoxy-3, 5-dimethylphenyl)-5, 7-di-tert-butyl-benzofuran-2-- one, 3- (3, 5-dimethyl-4-pivaloyloxyphenyl)-5, 7-di-tert-butyl-benzofuran-2-one.

Particulariy preferred conventional additives are those listed above under items 1 and/or 4.

Also the compound of the formula

is one of the preferred conventional additives which may additionally be incorporated into the polyolefin to be stabiiized.

The weight ratio of the total amount of components (A), (B), (C) and optionally (D1) and/or (D2) to the total amount of the conventional additives can be, for example, 100: 1 to 1: 100.

The examples below illustrate the invention in greater detail. All percentages and parts are by weight, unless stated otherwise.

Sterically hindered amine compounds used in the following Examptes 1 to 3: (For the polymeric compounds, the mean degree of polymerization is indicated in each case.) Compound 13: (&commat;Tinuvin770)

Compound 36-d : (#Sanduvor PR-31)

Compound 81: (#Tinuvin 622)

with mi being 5.1.

Compound 84-1 : (#Chimassorb 944)

with m4 being 4.5.

Mixture of the compounds 96-I and 96-II : (Preferably #Hostavin N30)

with m, 6 being 3.9 and m, s* being 4.2 and the weight ratio of (96-f) to (96-il) being 4: 1.

Compound fOO-A : (OUvasorb HA88 (Chemical Abstracts CAS No. 136 504-96-6)) A product obtainable by reacting an intermediate product, obtained by reaction of a polyamine of the formula (100a-I) with cyanuric chloride, with a compound of the formula (100b-I).

H, N---(CH)---NH--(CH,),---NH---(C--NH, -I)

Compound 101-1 : (Preferably #Uvasil 299)

with m2, being 5.8.

Compound 105: (#Goodrite UV 3150)

Compound 106: (#Goodrite UV 3159)

Exampte 1 : Light stabilization of injection molded 2 mm polypropylene plaques.

100 parts of polypropylene powder (melt flow index:-2.4 g/10 min at 2304C and 2160 g) are blended in a barrel mixer with 0.05 parts of pentaerythrityl-tetrakis (3- (3, 5-di-tert-butyl-4- hydroxyphenyl) propionate], 0.05 parts of tris [2, 4-di-tert-butylphenyl] phosphite, and the stabilizer system indicated in Tables 1 to 3. Then, the blend is compounded in an extruder at temperatures of 200 -2204C. The granules obtained on extrusion and granulation are transformed into 2 mm thick plaques at 240 -260 C in an automatic injection molding machine.

The plaques are mounted on sample holders and subjected to natural weathering in Florida (45 South, direct, approximately 140 kLy/year). Periodically, the carbonyl content of the samples is measured with an infrared spectrophotometer. The exposure time corresponding to formation of a carbonyl absorbance of 0.5 is a measure for the efficiency of the stabilizer system.

The values obtained are summarized in Tables 1 to 3.

The synergistic effect of the two coadditivs ( (1) and (2)) is determined by a comparison of the calculated To. value with the actually measured To. 5 value. The To. s values are calculated on the basis of the additivity law (B. Ranby and J. F. Rabek ; Photodegradation, Photooxidation and Photostabilization of Polymers, Principes and Applications, John Wiley & Sons, London, New York, Sydney, Toronto, 1975, pages 418 and 419) according to the following equation: Expected stabilizing activity = Stabilizing activity of 100 % (1) + stabilizing activity of 100 % (2) 2 There is a synergistic effect for the two coadditivs in question, when To. 5measurw-"To. scakLdated.

Table 1: Sterically hindered amine compound: 0.1 % of the compound 81

Coadditiv T0.5 calculated T0.5 measured (kLy) (kLy) 0.1 % of Ca-oxide 63 0.1 % of Zn-hydroxide-carbonate 81 0.05 % of Zn-hydroxide-carbonate + 86 72 0.05 % of Ca-oxide Table 2: Sterically hindered amine compound: 0.1 % of the compound 84-1

Coadditiv T TQ5 5ca < eubted (kLy) (kLy) 0.1 % of Ca-stearate 88 0.1 % of Ca-oxide 150 0. 1 % of hydrotalcite (&commat;DHT-4A) 144 4 0.1 /of Zn-hydroxide-carbonate 136 0.05 % of Ca-oxide + 180 147 0.05 % of hydrotalcite (#DHT-4A) 0.05 % of Zn-hydroxide-carbonate + 168 112 0.05 % of Ca-stearate 0.05 % of Zn-hydroxide-carbonate + 172 143 0.05 % of Ca-oxide Table 3 : Sterically hindered amine compound: 0.05 % of the compound 81 UV absorber: 0. 05 % of the compound of the formula

Coadditiv T0.5 calculated T0.5 measured (kLy) (kLy) 0.1 % of Ca-stearate 136 0.1 % of Ca-oxide 102 0.1 % of Ca-hydroxide 149 01 % of hydrotalcite (&commat;DHT-4A) 127 0.1 % of Zn-hydroxide-carbonate 121 0.1 % of Mg-stearate 216 0.1 % of Zn-stearate 200 0.1 % of Mg-acetylacetonate 202 0.1 % of Mg-oxide 176 0.1 % of Zn-oxide 70 0.1 % of Mg-hydroxide 146 0.1 % of dolomite (#Microdol Super) 77 0.1 % of Zn-acetylacetonate 68 0.05 % of hydrotalcite (#DHT-4A) + 116 114.5 0.05 % of Ca-oxide 0.05 % of Zn-hydroxide-carbonate + 182 128.5 0.05 % of Ca-stearate

0.05 % of Zn-hydroxide-carbonate 175 111. 5 0.05 % of Ca-oxide 0.05 % of dolomite (#Microdol Super) + 112 106.5 0.05 % of Ca-stearate 0.05 % of Mg-stearate + 252 159 0.05 % of Ca-oxide 0.05 % of Mg-stearate + 222 182. 5 0.05 % of Ca-hydroxide 0.05 % of Zn-stearate + 168 151 0.05 % of Ca-oxide 0.05 % of Mg-acetylacetonate + 240 152 0.05 % of Ca-oxide 0.05 % of Mg-acetylacetonate + 248 175. 5 0.05 % of Ca-hydroxide 0.05 % of Zn-acetylacetonate 97 85 0.05 % of Ca-oxide 0.05 % of Zn-acetylacetonate + 126 108. 5 0.05 % of Ca-hydroxide 0.05 % of Mg-oxide + 148 139 0. 05 % of Ca-oxide 0.05 % of Zn-oxide + 89 86 0.05 % of Ca-oxide 0.05 % of Ca-oxide + 137 124 0.05 % of Mg-hydroxide Exemple 2: Light stabilization of polypropylene tapes.

100 parts of polypropylene powder (melt flow index: 2 g/10 min at 230 C and 2160 g) are blended in a barrel mixer with 0.05 parts of pentaerythrityl tetrakis [3- (3, 5-di-tert-butyl-4- hydroxyphenyf) propionate], 0.05 parts of trist2, 4-di-tert-butylphenyl] phosphite and the stabilizer system indicated in Table 4. Then, the blend is compounded in an extruder at temperatures of 180 -220 C. The granules obtained on extrusion and granulation are transformed into films at 220 -260 C in a second extruder equipped with a flat sheet die. The films are cut into ribbons which are drawn to achieve a stretch ratio of 1: 6. The tapes obtained with this procedure are finally 50 prn thick and 2.5 mm wide.

*The tapes are mounted without tension on sample holders and exposed in a WEATHER OMETER Ci 65 (black panel temperature 63#2 C, without water-spraying). Penodicaity, the tensile strength of the exposed tapes is measured. The exposure time corresponding to a loss of 50 % (Tgo) of the initial tensile strength is a measure for the efficiency of the stabilizer system.

The values obtained are summarized in Table 4.

The determination of the synergistic effect of the two coadditivs is carried out as described in Example 1.

Table 4: 0.4 % of titanium dioxide (rutile)

Tsomeasured (hours to 50 % retained tensile strength) Sterically hindered 0.05 % of amine compound Ca-stearate + 0.1 % of 0.1 % of 0. 05 % of Ca-stearate hydrotalcite Tso sbted hydrotalcite (*DHT-4A) (#DHT-4A) O. 05% of compound 13 3360 2150 1920 2035 0.10 % of compound 13 7600 5600 4300 4950 0. 20 % of compound 13 14500 13500 10zoo 11750 Example 3: Light stabilization of compression molded 0.5 mm polypropylene copolymer films 100 parts of unstabilized polypropylene powder (melt flow index:-6 g/10 min at 230 C and 2160 g) are homogenized at 200 C for 10 min in a Brabender plastograph with 0.05 parts of pentaerythrityl-tetrakis (3- (3, 5-di-tert-butyl-4-hydroxyphenyt) propionate], 0.10 parts of tris [2,4di-tert-butylphenyl] phosphite, and the stabilizer system indicated in Tables 5 to 8. The material thus obtained is compression molded in a laboratory press between two aluminum foils for 6 min at 260 C to a 0.5 mm thick film which is cooled immediately to room temperature in a water-cooled press. Samples of 60 mm x 25 mm are cut out of these 0.5 mm films and exposed in a WEATHER-OMETER Ci 65 (black panel temperature 63+2 C, without water-spraying). Periodically, these samples are removed from the exposure apparatus and their carbonyt content is measured with an infrared spectrophotometer. The exposure time corresponding to formation of a carbonyl absorbance of 0.1 is a measure for the efficiency of the stabilizer system. The values obtained are summarized in Tables 5 to 8.

Table 5: 0.1 % of Ca-stearate, 0.1 % of Mg-stearate and 0.1 % of the compound of the formula

0.1 % of sterically hindered tao. 1 compound (h) Compound 101-1 3680 Compound 100-A 3200 Mixture of compounds 96-l and 96-il 2480

Compound105 2920 Compound106 2600 Compound36-d 3080 Table 6 : 0.1 % of Ca-stearate, 0.1 % of hydrotalcite (DHT-4A) and 0.1 % of the compound of the formula

0.1 % of sterically hindered @0.1 compound (h) Compound 101-1 3680 Compound 100-A 3460 Compound 106 4400 Table : 0.1 % of Ca-stearate, 0.1 % of Mg-stearate and 0.5 % of TiO2 (rutile)

0.1 % of sterically hindered lo. i compound (h)

Compound 101-I 4530 Compound 100-A 3340 Compound 105 3280 Compound 106 3320 Compound36-d 3340 Table 8 : 0.1 % of Ca-stearate, 0.1 % of hydrotalcite (#DHT-4A) and 0.1 % of Ti02 (rutile)

0.1 % of sterically hindered amine"' compound(h) Compound 101-1 4120 Compound 100-A 4080 Compound 105 3905 Compound 1063955

Claims (3)

Claims 1. A composition comprising a polyolefin and a stabilizer mixture containing (A) a sterically hindered amine compound selected from the group consisting of the compounds 13, 14,36-a, 36-b, 36-d, 96-I, 96-II, 100-A, 101-l, 105 and 106;

1, 2,3,4-tetrakis {2,2,6,6-tetramethylpiperidin-4-yloxycarbonyl} butane (36-a) 1,2,3,4-tetrakis {1,2,2,6,6-pentamethylpiperidin-4-yloxycarbonyl} butane (36-b)

with m16 and m16* being a number from 2 to 50; a product (100-A) obtainable by reacting an intermediate product, obtained by reaction of a polyamine of the formula (100a-I) with cyanuric chloride, with a compound of the formula (100b-I) ; H2N- (CH2)3-NH-(CH2)2-NH-(CH2)3-NH2 (100a-1)

with m21 being a number from 1 to 20;

(B) an organic sait of Ca or an inorganic salt of Ca; and (C) an organic salt of Mg, an inorganic salt of Mg, an organic salt of Zn or an inorganic salt of Zn ; with the proviso that the polyolefin is polypropylene, when component (A) of the stabilizer mixture is the compound 96-1, 96-11 or 100-A.

2. A composition according to claim 1 wherein the polyolefin is polyethylene, polypropylene, a polyethylene copolymer or a polypropylene copolymer.

3. A method for stabilizing a polyolefin against degradation induced by light, heat or oxidation, which comprises incorporating into the polyolefin a stabilizer mixture as defined in claim 1.