KR100530090B1 - Stabilizer Mixes for Organics - Google Patents

Abstract

Organic materials having excellent stability against oxidation, thermal or photo-induced degradation include, as stabilizers, one or more benzofuran-2-one type compounds, one or more organic phosphite or phosphonite type compounds, one or more phenolic antioxidant type compounds. And one or more sterically hindered amine compounds.

Description

Stabilizer Mixture For Organic Materials

The present invention relates to organic materials susceptible to oxidation, heat or light-induced degradation, and at least one benzofuran-2-one type compound, at least one phosphite or phosphonite type compound, at least one phenolic antioxidant type compound and Compositions comprising one or more sterically hindered amine compounds; And to the use of the composition for stabilizing organic materials against oxidation, heat or photo-induced decomposition.

The use of benzofuran-2-one type compounds as stabilizers for organic polymers is described, for example, in US 4,325,863; US 4,388,244; US 5,175,312; US 5,252,643; US 5,216,052; US 5,369,159; US 5,488,117; US 5,356,966; US 5,367,008; US 5,428,162; Known from US 5,428,177 or US 5,516,920.

Organic phosphites, phosphonites and phosphoramides are known in the art as co-stabilizers, secondary antioxidants and process stabilizers for polyolefins. Examples of such known phosphite stabilizers are described in R. Gachter / H. Muller (eds.), Plastics Additives Handbook, 3rd ed., P. 47, Hanser, Munich 1990.

U.S. Patent 4,360,617 discloses a stabilizer mixture comprising symmetric triarylphosphite and certain phenolic antioxidants for certain organic materials such as polyurethane, polyacrylonitrile, polyamide 12 or It is described as being particularly suitable for protecting polystyrene.

In particular, hindered amines comprising compounds containing 2,2,6,6-tetramethylpiperidyl groups are known as hindered amine stabilizers (HALS).

Known stabilizers do not meet all of the high requirements for stabilizers, in particular, which meet improvements in shelf life, water absorption, hydrolysis sensitivity, processing stability, color properties, volatility, mobility, compatibility and protection against light. . As a result, there is a continuing need for effective stabilizers for organic materials susceptible to oxidation, heat and / or light-induced degradation.

Stabilizer mixtures comprising at least one benzofuran-2-one type compound, at least one organic phosphite or phosphonite type compound, at least one phenolic antioxidant type compound and at least one sterically hindered amine type compound are oxidized, heat or light It is described as being particularly suitable as a stabilizer for organic substances susceptible to induced degradation.

Accordingly, the present invention provides a composition comprising:

a) organic matter susceptible to oxidation, heat or light-induced degradation;

b) at least one benzofuran-2-one type compound,

c) at least one compound selected from the group of organic phosphites or phosphonites,

d) at least one compound selected from the group of phenolic antioxidants and

e) at least one compound selected from the group of sterically hindered amines.

An important composition is one comprising as component (b) a compound of formula (1):

Where n is 1,

R ₁ is unsubstituted or C ₁ -C ₄ alkyl-, C ₁ -C ₄ alkoxy-, C ₁ -C ₄ alkylthio-, hydroxy-, halo-, amino-, C ₁ -C ₄ alkylamino-, Phenylamino- or di (C ₁ -C ₄ alkyl) amino-substituted naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetra Hydro-1-naphthyl, thienyl, benzo [b] thienyl, naphtho [2,3-b] thienyl, thianthrenyl, dibenzofuryl, chromenyl, xanthenyl, phenoxatiinyl, pi Rollyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolinyl, isoindolyl, indolyl, indazolyl, furinyl, quinolzynyl, isoquinolyl, quinolyl, phthala Genyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnaolinyl, putridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl , Isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, pool A carbonyl or fluorescein page noksa or possess, or R ₁ is for a radical of formula (2),

And,

if n is 2,

R ₁ is unsubstituted or C ₁ -C ₄ alkyl- or hydroxy-substituted phenylene or naphthylene; Or -R ₁₂ -XR _13- ,

R ₂ , R ₃ , R ₄ and R ₅ are independently of each other hydrogen, chlorine, hydroxy, C ₁ -C ₂₅ alkyl, C ₇ -C ₉ phenylalkyl, unsubstituted or C ₁ -C ₄ alkyl-substituted phenyl; Unsubstituted or C ₁ -C ₄ alkyl-substituted C ₅ -C ₈ cycloalkyl; C ₁ -C ₁₈ alkoxy, C ₁ -C ₁₈ alkylthio, C ₁ -C ₄ alkylamino, di (C ₁ -C ₄ alkyl) amino, C ₁ -C ₂₅ alkanoyloxy, C ₁ -C ₂₅ alkanoyl Amino, C ₃ -C ₂₅ alkenoyloxy, oxygen in the middle of the chain, sulfur or C ₃ -C ₂₅ alkanoyloxy comprising; C ₆ -C ₉ cycloalkylcarbonyloxy, benzoyloxy or C ₁ -C ₁₂ alkyl-substituted benzoyloxy; Or other radicals R ₂ and R ₃ or the radicals R ₃ and R ₄ or the radicals R ₄ and R ₅ together with the carbon atoms attached thereto form a benzo ring, wherein R ₄ is additionally-(CH ₂ ) _{if p} -COR ₁₅ or-(CH ₂ ) _q OH or if R ₃ , R ₅ and R ₆ are hydrogen, R ₄ is additionally a radical of formula (3),

R ₁ is defined as described above when n = 1,

R ₆ is hydrogen or a radical of formula (4),

R ₄ is not a radical of formula (3) and R ₁ is defined as described above when n = 1,

R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are independently of each other hydrogen, halogen, hydroxy, C ₁ -C ₂₅ alkyl, oxygen, sulfur or C ₂ -C ₂₅ alkyl comprising; C ₁ -C ₂₅ alkoxy, oxygen, sulfur or C ₂ -C ₂₅ alkoxy comprising; C ₁ -C ₂₅ alkylthio, C ₃ -C ₂₅ alkenyl, C ₃ -C ₂₅ alkenyloxy, C ₃ -C ₂₅ alkynyl, C ₃ -C ₂₅ alkynyloxy, C ₇ -C ₉ phenylalkyl, C ₇ -C ₉ phenylalkoxy, unsubstituted or C ₁ -C ₄ alkyl-substituted phenyl; Unsubstituted or C ₁ -C ₄ alkyl-substituted phenoxy; Unsubstituted or C ₁ -C ₄ alkyl-substituted C ₅ -C ₈ cycloalkyl; Unsubstituted or C ₁ -C ₄ alkyl-substituted C ₅ -C ₈ cycloalkoxy; C ₁ -C ₄ alkylamino, di (C ₁ -C ₄ alkyl) amino, C ₁ -C ₂₅ alkanoyl, oxygen, sulfur or C ₃ -C ₂₅ alkanoyl comprising; C ₁ -C ₂₅ alkanoyloxy, oxygen, sulfur or C ₃ -C ₂₅ alkanoyloxy comprising; C ₁ -C ₂₅ alkanoylamino, C ₃ -C ₂₅ alkenoyl, oxygen, sulfur or C ₃ -C ₂₅ alkenoyl comprising; C ₃ -C ₂₅ alkenoyloxy, oxygen, sulfur or C ₃ -C ₂₅ alkenoyloxy comprising; C ₆ -C ₉ cycloalkylcarbonyl, C ₆ -C ₉ cycloalkylcarbonyloxy, benzoyl or C ₁ -C ₁₂ alkyl-substituted benzoyl; Benzoyloxy or C ₁ -C ₁₂ alkyl-substituted benzoyloxy; or Or else, in formula (2), the radicals R ₇ and R ₈ or the radicals R ₈ and R ₁₁ join together with the carbon atoms attached to them to form a benzo ring,

R ₁₂ and R ₁₃ are independently of each other unsubstituted or C ₁ -C ₄ alkyl-substituted phenylene or naphthylene,

R ₁₄ is hydrogen or C ₁ -C ₈ alkyl,

R ₁₅ is hydroxy, , C ₁ -C ₁₈ alkoxy or ego,

R ₁₆ and R ₁₇ are independently of each other hydrogen, CF ₃ , C ₁ -C ₁₂ alkyl or phenyl, or R ₁₆ and R ₁₇ are unsubstituted or C ₁ -C ₄ alkyl together with the C atom attached thereto; To form one to three substituted C ₅ -C ₈ cycloalkylidene rings;

R ₁₈ and R ₁₉ are independently of each other hydrogen, C ₁ -C ₄ alkyl or phenyl,

R ₂₀ is hydrogen or C ₁ -C ₄ alkyl,

R ₂₁ is hydrogen, unsubstituted or C ₁ -C ₄ alkyl-substituted phenyl; C ₁ -C ₂₅ alkyl, oxygen, sulfur or C ₂ -C ₂₅ alkyl comprising; C ₇ -C ₉ phenylalkyl substituted one to three times by C ₁ -C ₄ alkyl on an unsubstituted or phenyl radical; Substituted 1-3 times with C ₁ -C ₄ alkyl on an unsubstituted or phenyl radical, with oxygen, sulfur or C ₇ -C ₂₅ phenylalkyl, or, or any other radical R ₂₀ and R ₂₁ are unsubstituted with one carbon atom attached to these, or C ₁ -C ₄ alkyl, one to three times substituted by a C ₅ -C, including Forms a ₁₂ cycloalkylene ring;

R ₂₂ is hydrogen or C ₁ -C ₄ alkyl,

R ₂₃ is hydrogen, C ₁ -C ₂₅ alkanoyl, C ₃ -C ₂₅ alkenoyl, oxygen, sulfur or C ₃ -C ₂₅ alkanoyl comprising; C ₂ -C ₂₅ alkanoyl substituted by di (C ₁ -C ₆ alkyl) phosphonate groups; C ₆ -C ₉ cycloalkylcarbonyl, tenoyl, furoyl, benzoyl or C ₁ -C ₁₂ alkyl-substituted benzoyl;

or ego,

R ₂₄ and R ₂₅ are independently of each other hydrogen or C ₁ -C ₁₈ alkyl,

R ₂₆ is hydrogen or C ₁ -C ₈ alkyl,

R ₂₇ is a direct bond, C ₁ -C ₁₈ alkylene, oxygen, sulfur or C ₂ -C ₁₈ alkylene comprising a; C ₂ -C ₁₈ alkenylene, C ₂ -C ₂₀ alkylidene, C ₇ -C ₂₀ phenylalkylidene, C ₅ -C ₈ cycloalkylene, C ₇ -C ₈ bicycloalkylene, unsubstituted or C _1- C ₄ alkyl-substituted phenylene or or ego,

R ₂₈ is hydroxy, , C ₁ -C ₁₈ alkoxy or ego,

R ₂₉ is oxygen, -NH- or ego,

R ₃₀ is C ₁ -C ₁₈ alkyl or phenyl,

R ₃₁ is hydrogen or C ₁ -C ₁₈ alkyl,

M is a r-valent metal cation,

X is a direct bond, oxygen, sulfur or -NR _31- ,

n is 1 or 2,

p is 0, 1 or 2,

q is 1, 2, 3, 4, 5 or 6,

r is 1, 2 or 3, and

s is 0, 1 or 2.

Unsubstituted or C ₁ -C ₄ alkyl-, C ₁ -C ₄ alkoxy-, C ₁ -C ₄ alkylthio-, hydroxy-, halo-, amino-, C ₁ -C ₄ alkylamino-, phenylamino- Or di (C ₁ -C ₄ alkyl) amino-substituted naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1 Naphthyl, thienyl, benzo [b] thienyl, naphtho [2,3-b] thienyl, thianthrenyl, dibenzofuryl, chromenyl, xanthenyl, phenoxatiinyl, pyrrolyl, imi Dazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolinyl, isoindolyl, indolyl, indazolyl, furinyl, quinolinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyl Lidinyl, quinoxalinyl, quinazolinyl, cinnaolinyl, putridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothia Zolyl, phenothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, pullulore Neyl or phenoxazinyl is for example 1-naphthyl, 2-naphthyl, 1-phenylamino-, 4-naphthyl, 1-methylnaphthyl, 2-methylnaphthyl, 1-methoxy-2-naphthyl , 2-methoxy-1-naphthyl, 1-dimethylamino-2-naphthyl, 1,2-dimethyl-4-naphthyl, 1,2-dimethyl-6-naphthyl, 1,2-dimethyl-7 Naphthyl, 1,3-dimethyl-6-naphthyl, 1,4-dimethyl-6-naphthyl, 1,5-dimethyl-2-naphthyl, 1,6-dimethyl-2-naphthyl, 1- Hydroxy-2-naphthyl, 2-hydroxy-1-naphthyl, 1,4-dihydroxy-2-naphthyl, 7-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl , 3-benzo [b] thienyl, 5-benzo [b] thienyl, 2-benzo [b] thienyl, 4-dibenzofuryl, 4,7-dibenzofuryl, 4-methyl-7-dibenzo Furyl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl, 2-phenoxatiinyl, 2,7-phenoxathinyl, 2-pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl-4-imidazolyl, 2-ethyl -5-imidazolyl, 3-pyrazolyl, 1- Tyl-3-pyrazolyl, 1-propyl-4-pyrazolyl, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2- Methyl-1-isoindolyl, 1-methyl-2-indolyl, 1-methyl-3-indolyl, 1,5-dimethyl-2-indolyl, 1-methyl-3-indazolyl, 2,7- Dimethyl-8-furinyl, 2-methoxy-7-methyl-8-furinyl, 2-quinolinyl, 3-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, isoquinolyl, 3 -Methoxy-6-isoquinolyl, 2-quinolyl, 6-quinolyl, 7-quinolyl, 2-methoxy-3-quinolyl, 2-methoxy-6-quinolyl, 6-phthalazinyl , 7-phthalazinyl, 1-methoxy-6-phthalazinyl, 1,4-dimethoxy-6-phthalazinyl, 1,8-naphthyridin-2-yl, 2-quinoxalinyl, 6- Quinoxalinyl, 2,3-dimethyl-6-quinoxalinyl, 2,3-dimethoxy-6-quinoxalinyl, 2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino-6-quinazoli Nilyl, 3-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 3-methoxy-7-cinnolinyl, 2-phthyridinyl, 6-phthyridinyl, 7-phthyridinyl, 6 , 7-D Oxy-2-pterridinyl, 2-carbazolyl, 3-carbazolyl, 9-methyl-2-carbazolyl, 9-methyl-3-carbazolyl, β-carbolin-3-yl, 1 -Methyl-β-carbolin-3-yl, 1-methyl-β-carboline-6-yl, 3-phenantridinyl, 2-acridinyl, 3-acridinyl, 2-ferimidinyl, 1 -Methyl-5-ferimidinyl, 5-phenanthrolinyl, 6-phenanthrolinyl, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2 -Phenothiazinyl, 3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 4-methyl-3-furazanyl, 2- Phenoxazinyl or 10-methyl-2-phenoxazinyl.

Especially preferred are unsubstituted or C ₁ -C ₄ alkyl-, C ₁ -C ₄ alkoxy-, C ₁ -C ₄ alkylthio-, hydroxy-, phenylamino- or di (C ₁ -C ₄ alkyl) amino- Substituted naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo [b] thier Neyl, naphtho [2,3-b] thienyl, thianthrenyl, dibenzofuryl, chromenyl, xanthenyl, phenoxatiinyl, pyrrolyl, isoindoleyl, indolyl, phenothiazinyl, biphenyl , Terphenyl, pulluorenyl or phenoxazinyl, eg, 1-naphthyl, 2-naphthyl, 1-phenylamino-4-naphthyl, 1-methylnaphthyl, 2-methylnaphthyl, 1-methoxy -2-naphthyl, 2-methoxy-1-naphthyl, 1-dimethylamino-2-naphthyl, 1,2-dimethyl-4-naphthyl, 1,2-dimethyl-6-naphthyl, 1, 2-dimethyl-7-naphthyl, 1,3-dimethyl-6-naphthyl, 1,4-dimethyl-6-naphthyl, 1,5-dimethyl-2-naphthyl, 1,6-dimethyl-2- Naphthyl, 1-hydroxy-2-naphthyl, 2-hydroxy-1-naphthyl, 1, 4-dihydroxy-2-naphthyl, 7-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl, 3-benzo [b] thienyl, 5-benzo [b] thienyl, 2 -Benzo [b] thienyl, 4-dibenzofuryl, 4,7-dibenzofuryl, 4-methyl-7-dibenzofuryl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3- Xanthenyl, 2-pyrrolyl, 3-pyrrolyl, 2-phenothiazinyl, 3-phenothiazinyl, 10-methyl-3-phenothiazinyl.

Halogen (halo) is, for example, chlorine, bromine or iodine. Preferably chlorine.

Alkanoyl having 25 carbon atoms or less may be a straight or branched radical, such as formyl, acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl , Dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, octadecanoyl, aicosanoyl or docosanoyl. Preference is given to alkanoyl having 2 to 18, in particular 2 to 12, for example 2 to 6 carbon atoms. Acetyl is particularly preferred.

C ₂ -C ₂₅ alkanoyl substituted by di (C ₁ -C ₆ alkyl) phosphonate groups is, for example, (CH ₃ CH ₂ O) ₂ POCH ₂ CO—, (CH ₃ O) ₂ POCH ₂ CO—, (CH ₃ CH ₂ CH ₂ CH ₂ O) ₂ POCH ₂ CO-, (CH ₃ CH ₂ O) ₂ POCH ₂ CH ₂ CO-, (CH ₃ O) ₂ POCH ₂ CH ₂ CO-, (CH ₃ CH ₂ CH ₂ CH ₂ O) ₂ POCH ₂ CH ₂ CO-, (CH ₃ CH ₂ O) ₂ PO (CH ₂ ) ₄ CO-, (CH ₃ CH ₂ O) ₂ PO (CH ₂ ) ₈ CO- or (CH ₃ CH ₂ O) ₂ PO (CH ₂ ) ₁₇ CO—.

Alkanoyloxy having up to 25 carbon atoms is a straight or branched chain radical such as formyloxy, acetoxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, octanoyloxy, no Nanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy, tridecanoyloxy,

Tetradecanoyloxy, pentadecanoyloxy, hexadecanoyloxy, heptadecanoyloxy, octadecanoyloxy, aicosanoyloxy or docosanoyloxy. Preferred are alkanoyloxy having 2 to 18, especially 2 to 12, such as 2 to 6 carbon atoms. Acetoxy is particularly preferred.

Alkenoyl having 3 to 25 carbon atoms may be a straight or branched chain radical, such as propenoyl, 2-butenoyl, 3-butenoyl, isobutenoyl, n-2,4-pentadienoyl, 3-methyl- 2-butenoyl, n-2-octenoyl, n-2-dodecenoyl, iso-dodecenoyl, oleyl, n-2-octadecenoyl or n-4-octadecenoyl. Preference is given to alkenoyl having 3 to 18, especially 3 to 12, for example 3 to 6, especially 3 to 4 carbon atoms.

Oxygen, sulfur or in the middle of the chain C ₃ -C ₂₅ alkenoyl comprising for example CH ₃ OCH ₂ CH ₂ CH═CHCO— or CH ₃ OCH ₂ CH ₂ OCH═CHCO—.

Alkenoyloxy having 3 to 25 carbon atoms is a straight or branched chain radical, such as propenylyl, 2-butenoyloxy, 3-butenoyloxy, isobutenoyloxy, n-2,4-pentadienoyl Oxy, 3-methyl-2-butenoyloxy, n-2-octenoyloxy, n-2-dodecenoyloxy, iso-dodecenoyloxy, oleoyloxy, n-2-octadecenoyloxy or n-4-octadecenoyloxy. Preferred are alkenoyloxy having 3 to 18, especially 3 to 12, such as 3 to 6, especially 3 to 4 carbon atoms.

Oxygen, sulfur or in the middle of the chain C ₃ -C ₂₅ alkenoyloxy comprising for example CH ₃ OCH ₂ CH ₂ CH═CHCOO— or CH ₃ OCH ₂ CH ₂ OCH═CHCOO—.

Oxygen, sulfur or in the middle of the chain C ₃ -C ₂₅ alkanoyl comprising, for example, CH ₃ -O-CH ₂ CO-, CH ₃ -S-CH ₂ CO-, CH ₃ -NH-CH ₂ CO-, CH ₃ -N (CH ₃ ) -CH ₂ CO-, CH ₃ -O-CH ₂ CH ₂ -O-CH ₂ CO-, CH _3- (O-CH ₂ CH _2- ) ₂ O-CH ₂ CO-, CH _3- (O- CH ₂ CH _2- ) ₃ O-CH ₂ CO-, or CH _3- (O-CH ₂ CH _2- ) ₄ O-CH ₂ CO-.

Oxygen, sulfur or in the middle of the chain C ₃ -C ₂₅ alkanoyloxy comprising, for example, CH ₃ -O-CH ₂ COO-, CH ₃ -S-CH ₂ COO-, CH ₃ -NH-CH ₂ COO-, CH ₃ -N (CH ₃ ) -CH ₂ COO-, CH ₃ -O-CH ₂ CH ₂ -O-CH ₂ COO-, CH _3- (O-CH ₂ CH _2- ) ₂ O-CH ₂ COO-, CH _3- (O —CH ₂ CH ₂ —) ₃ O—CH ₂ COO—, or CH ₃ — (O—CH ₂ CH ₂ —) ₄ O—CH ₂ COO—.

C ₆ -C ₉ cycloalkylcarbonyl is, for example, cyclohexylcarbonyl, cycloheptylcarbonyl or cyclooctylcarbonyl. Cyclohexylcarbonyl is preferred.

C ₆ -C ₉ cycloalkylcarbonyloxy is, for example, cyclohexylcarbonyloxy, cycloheptylcarbonyloxy or cyclooctylcarbonyloxy. Cyclohexylcarbonyloxy is preferred.

C ₁ -C ₁₂ alkyl-substituted benzoyl, preferably comprising 1 to 3, in particular 1 or 2 alkyl groups, are for example o-, m- or p-methylbenzoyl, 2,3-dimethylbenzoyl, 2,4- Dimethylbenzoyl, 2,5-dimethylbenzoyl, 2,6-dimethylbenzoyl, 3,4-dimethylbenzoyl, 3,5-dimethylbenzoyl, 2-methyl-6-ethylbenzoyl, 4-tert-butylbenzoyl, 2- Ethylbenzoyl, 2,4,6-trimethylbenzoyl, 2,6-dimethyl-4-tert-butylbenzoyl or 3,5-di-tert-butylbenzoyl. Preferred substituents are C ₁ -C ₈ alkyl, in particular C ₁ -C ₄ alkyl.

C ₁ -C ₁₂ alkyl-substituted benzoyloxy, preferably comprising 1 to 3, in particular 1 or 2 alkyl groups, are for example o-, m- or p-methylbenzoyloxy, 2,3-dimethylbenzoyloxy, 2 , 4-dimethylbenzoyloxy, 2,5-dimethylbenzoyloxy, 2,6-dimethylbenzoyloxy, 3,4-dimethylbenzoyloxy, 3,5-dimethylbenzoyloxy, 2-methyl-6-ethyl-benzoyloxy, 4-tert-butylbenzoyloxy, 2-ethyl-benzoyloxy, 2,4,6-trimethylbenzoyloxy, 2,6-dimethyl-4-tert-butylbenzoyloxy or 3,5-di-tert- Butylbenzoyloxy. Preferred substituents are C ₁ -C ₈ alkyl, in particular C ₁ -C ₄ alkyl.

Alkyl having 25 carbon atoms or less is a straight or branched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, secondary-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n -Pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl , 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodec Yarn, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, icosyl or docosyl. One of the preferred meanings of R ₂ and R ₄ is, for example, C ₁ -C ₁₈ alkyl. Particularly preferred meaning of R ₄ is C ₁ -C ₄ alkyl.

Alkenyl having 3 to 25 carbon atoms may be a straight or branched chain radical such as propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2- Butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preferably alkenyl having 3 to 18, especially 3 to 12, such as 3 to 6, especially 3 to 4 carbon atoms.

Alkenyloxy having 3 to 25 carbon atoms is a straight or branched chain radical such as propenyloxy, 2-butenyloxy, 3-butenyloxy, isobutenyloxy, n-2,4-pentadienyloxy, 3-methyl-2-butenyloxy, n-2-octenyloxy, n-2-dodecenyloxy, iso-dodecenyloxy, oleyloxy, n-2-octadecenyloxy or n-4-octa Decenyloxy. Preferred are alkenyl having 3 to 18, especially 3 to 12, such as 3 to 6, especially 3 to 4 carbon atoms.

Alkynyl having 3 to 25 carbon atoms may be a straight or branched chain radical such as propynyl (-CH ₂ -C≡CH), 2-butynyl, 3-butynyl, n-2-octynyl or n-2 It's dodecynyl. Preferred are alkynyl having 3 to 18, especially 3 to 12, for example 3 to 6, especially 3 to 4 carbon atoms.

Alkynyloxy having 3 to 25 carbon atoms is a straight or branched chain radical such as propynyloxy (-OCH ₂ -C≡CH), 2-butynyloxy, 3-butynyloxy, n-2-octynyl Oxy or n-2-dodecynyloxy. Preferred are alkynyloxy having 3 to 18, especially 3 to 12, such as 3 to 6, especially 3 to 4 carbon atoms.

Oxygen, sulfur or in the middle of the chain C ₂ -C ₂₅ alkyl comprising, for example, CH ₃ —O—CH ₂ —, CH ₃ —S—CH ₂ —, CH ₃ —NH—CH ₂ —, CH ₃ —N (CH ₃ ) —CH ₂ -, CH ₃ -O-CH ₂ CH ₂ -O-CH _2- , CH _3- (O-CH ₂ CH _2- ) ₂ O-CH _2- , CH _3- (O-CH ₂ CH _2- ) ₃ O-CH _2- , or CH _3- (O-CH ₂ CH _2- ) ₄ O-CH _2- .

C ₇ -C ₉ phenylalkyl is for example benzyl, α-methylbenzyl, α, α-dimethylbenzyl or 2-phenylethyl. Preference is given to benzyl and α, α-dimethylbenzyl.

C ₇ -C ₉ phenylalkyl unsubstituted or substituted 1-3 times with C ₁ -C ₄ alkyl on a phenyl radical, for example benzyl, α-methylbenzyl, α, α-dimethylbenzyl, 2-phenylethyl, 2 -Methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzyl or 4-tert-butylbenzyl. Benzyl is preferred.

Substituted 1-3 times with C ₁ -C ₄ alkyl on an unsubstituted or phenyl radical, with oxygen, sulfur or C ₇ -C ₂₅ phenylalkyl comprising straight or branched chain radicals such as phenoxymethyl, 2-methylphenoxymethyl, 3-methylphenoxymethyl, 4-methylphenoxymethyl, 2,4-dimethylphenoxymethyl , 2,3-dimethylphenoxymethyl, phenylthiomethyl, N-methyl-N-phenylmethyl, N-ethyl-N-phenylmethyl, 4-tert-butylphenoxymethyl, 4-tert-butylphenoxy Ethoxymethyl, 2,4-di-tert-butylphenoxymethyl, 2,4-di-tert-butylphenoxyethoxymethyl, phenoxyethoxyethoxyethoxymethyl, benzyloxymethyl, benzyloxy Ethoxymethyl, N-benzyl-N-ethylmethyl or N-benzyl-N-isopropylmethyl.

C ₇ -C ₉ phenylalkoxy is for example benzyloxy, α-methylbenzyloxy, α, α-dimethylbenzyloxy or 2-phenylethoxy. Benzyloxy is preferred.

Preferably C ₁ -C ₄ alkyl substituted phenyls containing 1 to 3, in particular 1 to 2 alkyl groups are for example o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl , 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl Or 2,6-diethylphenyl.

C ₁ -C ₄ alkyl substituted phenoxy, preferably containing 1 to 3, especially 1 to 2 alkyl groups, for example o-, m- or p-methylphenoxy, 2,3-dimethylphenoxy, 2 , 4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2-methyl-6-ethylphenoxy, 4 -Tert-butylphenoxy, 2-ethylphenoxy, 2,6-diethylphenoxy.

Unsubstituted or C ₁ -C ₄ alkyl-substituted C ₅ -C ₈ cycloalkyls are, for example, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tertiary -Butylcyclohexyl, cycloheptyl or cyclooctyl. Preferred are cyclohexyl and tert-butylcyclohexyl.

Unsubstituted or C ₁ -C ₄ alkyl-substituted C ₅ -C ₈ cycloalkoxy is for example cyclopentoxy, methylcyclopentoxy, dimethylcyclopentoxy, cyclohexoxy, methylcyclohexoxy, dimethylcyclohexoxy, Trimethylcyclohexoxy, tert-butylcyclohexoxy, cycloheptoxy or cyclooctoxy. Cyclohexoxy and tert-butylcyclohexoxy are preferred.

Alkoxy having up to 25 carbon atoms is a straight or branched chain radical such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy , Octoxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. Preferred are alkoxy having 1 to 12, especially 1 to 8, for example 1 to 6 carbon atoms.

Oxygen, sulfur or in the middle of the chain C ₂ -C ₂₅ alkoxy comprising, for example, CH ₃ -O-CH ₂ CH ₂ O-, CH ₃ -S-CH ₂ CH ₂ O-, CH ₃ -NH-CH ₂ CH ₂ O-, CH ₃ -N (CH ₃ ) -CH ₂ CH ₂ O-, CH ₃ -O-CH ₂ CH ₂ -O-CH ₂ CH ₂ O-, CH _3- (O-CH ₂ CH _2- ) ₂ O-CH ₂ CH ₂ O-, CH _3- (O-CH ₂ CH _2- ) ₃ O-CH ₂ CH ₂ O-, or CH _3- (O-CH ₂ CH _2- ) ₄ O-CH ₂ CH ₂ O- .

Alkylthio having up to 25 carbon atoms may be a straight or branched chain radical such as methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, pentylthio, isopentylthio, hexylthio, Heptylthio, octylthio, decylthio, tetradecylthio, hexadecylthio or octadecylthio. Preference is given to alkylthio having 1 to 12, especially 1 to 8, such as 1 to 6 carbon atoms.

Alkylamino having up to 4 carbon atoms is a straight or branched chain radical such as methylamino, ethylamino, propylamino, isopropylamino, n-butylamino, isobutylamino or tert-butylamino.

Di (C ₁ -C ₄ alkyl) amino is a straight or branched chain radical having two radicals independent of each other such as dimethylamino, methylethylamino, diethylamino, methyl-n-propylamino, methylisopropylamino, methyl- n-butylamino, methylisobutylamino, ethylisopropylamino, ethyl-n-butylamino, ethylisobutylamino, ethyl tert-butylamino, diethylamino, diisopropylamino, isopropyl-n-butyl Amino, isopropylisobutylamino, di-n-butylamino or diisobutylamino.

Alkanoylamino having up to 25 carbon atoms are linear or branched radicals, such as formylamino, acetylamino, propionylamino, butanoylamino, pentanoylamino, hexanoylamino, heptanoylamino, octanoylamino, no Nanoylamino, decanoylamino, undecanoylamino, dodecanoylamino, tridecanoylamino, tetradecanoylamino, pentadecanoylamino, hexadecanoylamino, heptadecanoylamino, octadecanoylamino, aicosano Monoamino or docosanoylamino. Preferred are alkanoylamino having 2 to 18, especially 2 to 12, for example 2 to 6 carbon atoms.

C ₁ -C ₁₈ alkylene is a straight or branched radical, such as methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene or octadecamethylene . Preferred are C ₁ -C ₁₂ alkylenes, in particular C ₁ -C ₈ alkylene.

C ₁ -C ₄ alkyl-substituted C ₅ -C ₁₂ cycloalkylene rings, preferably containing 1 to 3, in particular 1 or 2 straight or branched alkyl group radicals, are for example cyclopentylene, methylcyclopentylene , Dimethylcyclopentylene, cyclohexylene, methylcyclohexylene, dimethylcyclohexylene, trimethylcyclohexylene, tert-butylcyclohexylene, cycloheptylene, cyclooctylene or cyclodecylene. Preferred are cyclohexylene and tert-butylcyclohexylene.

Oxygen, sulfur or in the middle of the chain C ₂ -C ₁₈ alkylene comprising, for example, —CH ₂ —O—CH ₂ —, —CH ₂ —S—CH ₂ —, —CH ₂ —NH—CH ₂ —, —CH ₂ —N (CH ₃ ) -CH _2- , -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 CH _2- ) ₃ O-CH ₂ -or -CH _2- (O-CH ₂ CH _2- ) ₄ O-CH ₂ -or -CH ₂ CH ₂ -S-CH ₂ CH _2- .

C ₂ -C ₁₈ alkenylene is, for example, vinylene, methylvinylene, octenylethylene or dodecenylethylene. Preferred are C ₂ -C ₈ alkenylene.

Alkylidenes having 2 to 20 carbon atoms are for example ethylidene, propylidene, butylidene, pentidene, 4-methylpentylidene, heptylidene, nonylidene, tridecylidene, nonadecyli Den, 1-methylethylidene, 1-ethylpropylidene or 1-ethylpentylidene. Preferred is C ₂ -C ₈ alkylidene.

Phenylalkylidene having 7 to 20 carbon atoms is, for example, benzylidene, 2-phenylethylidene or 1-phenyl-2-hexylidene. Preferred is C ₇ -C ₉ phenylalkylidene.

C ₅ -C ₈ cycloalkylene is a saturated hydrocarbon group having two free groups and one or more rings, for example cyclopentylene, cyclohexylene, cycloheptylene or cyclooctylene. Preferred is cyclohexylene.

C ₇ -C ₈ bicycloalkylene is for example bicycloheptylene or bicyclooctylene.

Unsubstituted or C ₁ -C ₄ alkyl-substituted phenylenes or naphthylenes are for example 1,2-, 1,3-, 1,4-phenylene, 1,2-, 1,3-, 1,4- , 1,6-, 1,7-, 2,6- or 2,7-naphthylene. 1,4-phenylene is preferred.

The C ₁ -C ₄ alkyl-substituted C ₅ -C ₈ cycloalkylidene rings which preferably contain 1 to 3 especially 1 or 2 straight or branched alkyl group radicals are for example cyclopentylidene, methylcyclopentylidene , Dimethylcyclopentylidene, cyclohexylidene, methylcyclohexylidene, dimethylcyclohexylidene, trimethylcyclohexylidene, tert-butylcyclohexylidene, cycloheptylidene or cyclooctylidene. Preferred are cyclohexylidene and tert-butylcyclohexylidene.

The mono-, di- or trivalent metal cations are preferably alkali metal, alkaline earth metal or aluminum cations such as Na ⁺ , K ⁺ , Mg ⁺⁺ , Ca ⁺⁺ or Al ⁺⁺⁺ .

Important compositions include when R is ₁ , R ₁ is unsubstituted phenyl or phenyl substituted at the para position by C ₁ -C ₁₈ alkylthio or (C ₁ -C ₄ alkyl) amino; 1- to 5-substituted alkylphenyl having up to 18 carbon atoms in total from 1 to 5 alkyl substituents; Or unsubstituted or C ₁ -C ₄ alkyl-, C ₁ -C ₄ alkoxy-, C ₁ -C ₄ alkylthio-, hydroxy- or amino-substituted naphthyl, biphenyl, terphenyl, phenanthryl, anthryl At least one compound of formula (1) which is fluorenyl, carbazolyl, thienyl, pyrrolyl, phenothiazinyl or 5,6,7,8-tetrahydronaphthyl as component (b).

Preferred are compositions comprising as component (b) one or more compounds of formula (1) defined as follows:

when n is 2,

R ₁ is -R ₁₂ -XR _13- ,

R ₁₂ and R ₁₃ are phenylene,

X is oxygen or -NR _31- , and

R ₃₁ is C ₁ -C ₄ alkyl.

Preferred are compositions comprising as component (b) one or more compounds of formula (1) defined as follows:

when n is 1,

R ₁ is unsubstituted or C ₁ -C ₄ alkyl-, C ₁ -C ₄ alkoxy-, C ₁ -C ₄ alkylthio-, hydroxy-, halo-, amino- or C ₁ -C ₄ alkylamino- or Di (C ₁ -C ₄ alkyl) amino-substituted naphthyl, phenanthryl, thienyl, dibenzofuryl, carbazolyl, fluorenyl or a radical of formula (2),

(2)

R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ independently of one another are hydrogen, chlorine, bromine, hydroxy, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkyl comprising oxygen or sulfur in the middle of the chain; C ₁ -C ₁₈ alkoxy, C ₂ -C ₁₈ alkoxy including oxygen or sulfur in the middle of the chain; C ₁ -C ₁₈ alkylthio, C ₃ -C ₁₂ alkenyloxy, C ₃ -C ₁₂ alkynyloxy, C ₇ -C ₉ phenylalkyl, C ₇ -C ₉ phenylalkoxy, unsubstituted or C ₁ -C ₄ Alkyl-substituted phenyl; Phenoxy, cyclohexyl, C ₅ -C ₈ cycloalkoxy, C ₁ -C ₄ alkylamino, di (C ₁ -C ₄ -alkyl) amino, C ₁ -C ₁₂ alkanoyl, containing oxygen or sulfur in the middle of the chain C ₃ -C ₁₂ alkanoyl; C ₁ -C ₁₂ alkanoyloxy, C ₃ -C ₁₂ alkanoyloxy comprising oxygen or sulfur in the middle of the chain; C ₁ -C ₁₂ alkanoylamino, C ₃ -C ₁₂ alkenoyl, C ₃ -C ₁₂ alkenoyloxy, cyclohexylcarbonyl, cyclohexylcarbonyloxy, benzoyl or C ₁ -C ₄ alkyl-substituted benzoyl; Benzoyloxy or C ₁ -C ₄ alkyl-substituted benzoyloxy; or Or else, in formula (2), the radicals R ₇ and R ₈ or the radicals R ₈ and R ₁₁ join together with the carbon atoms attached thereto to form a benzo ring,

R ₁₅ is hydroxy, C ₁ -C ₁₂ alkoxy or ego,

R ₁₈ and R ₁₉ are independently of each other hydrogen or C ₁ -C ₄ alkyl,

R ₂₀ is hydrogen,

R ₂₁ is hydrogen, phenyl, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkyl comprising oxygen or sulfur in the middle of the chain; C ₇ -C ₉ phenylalkyl, unsubstituted or substituted one to three times by C ₁ -C ₄ alkyl on the phenyl radical, or a C ₇ -C ₁₈ phenylalkyl containing oxygen or sulfur in the chain middle, or else The radicals R ₂₀ and R ₂₁ join together with the carbon atoms attached thereto to form a cyclohexylene ring which is unsubstituted or substituted one to three times with C ₁ -C ₄ alkyl;

R ₂₂ is hydrogen or C ₁ -C ₄ alkyl,

R ₂₃ is hydrogen, C ₁ -C ₁₈ alkanoyl, C ₃ -C ₁₈ alkenoyl, C ₃ -C ₁₂ alkanoyl including oxygen or sulfur in the middle of the chain; C ₂ -C ₁₂ alkanoyl substituted by di (C ₁ -C ₆ -alkyl) phosphonate groups; C ₆ -C ₉ cycloalkylcarbonyl, benzoyl,

or ego,

R ₂₄ and R ₂₅ are independently of each other hydrogen or C ₁ -C ₁₂ alkyl,

R ₂₆ is hydrogen or C ₁ -C ₄ alkyl,

R ₂₇ is C ₁ -C ₁₂ alkylene, C ₂ -C ₈ alkenylene, C ₂ -C ₈ alkylidene, C ₇ -C ₁₂ phenylalkylidene, C ₅ -C ₈ cycloalkylene or phenylene,

R ₂₈ is hydroxy, C ₁ -C ₁₂ alkoxy or ego,

R ₂₉ is oxygen or -NH-,

R ₃₀ is C ₁ -C ₁₈ alkyl or phenyl, and

s is 1 or 2.

Preferred are compositions comprising as component (b) one or more compounds of formula (1) defined as follows:

when n is 1,

R ₁ is phenanthryl, thienyl, dibenzofuryl, unsubstituted or C ₁ -C ₄ alkyl-substituted carbazolyl; Or fluorenyl; Or R ₁ is a radical of the formula (2),

(2)

R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ independently of one another are hydrogen, chlorine, hydroxy, C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ alkoxy, C ₁ -C ₁₈ alkylthio, C _3- C ₄ alkenyloxy, C ₃ -C ₄ alkynyloxy, phenyl, benzoyl, benzoyloxy or ego,

R ₂₀ is hydrogen,

R ₂₁ is hydrogen, phenyl or C ₁ -C ₁₈ alkyl, or other radicals R ₂₀ and R ₂₁ are cyclo unsubstituted or substituted one to three times with C ₁ -C ₄ alkyl with a carbon atom attached thereto; To form a hexylene ring;

R ₂₂ is hydrogen or C ₁ -C ₄ alkyl, and

R ₂₃ is hydrogen, C ₁ -C ₁₂ alkanoyl or benzoyl.

Especially preferred are compositions comprising as component (b) one or more compounds of the formula (1) defined as follows:

when n is 1,

R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are independently of each other hydrogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₄ alkylthio or phenyl.

Of particular interest are compositions comprising as component (b) one or more compounds of formula (1) defined as follows:

R ₂ , R ₃ , R ₄ and R ₅ independently of one another are hydrogen, chlorine, C ₁ -C ₁₈ alkyl, benzyl, C ₅ -C ₈ cycloalkyl, C ₁ -C ₁₈ alkoxy, C ₁ -C ₁₈ alkylthio , C ₁ -C ₁₈ alkanoyloxy, C ₁ -C ₁₈ alkanoylamino, C ₃ -C ₁₈ alkenoyloxy or benzoyloxy; Or other radicals R ₂ and R ₃ or the radicals R ₃ and R ₄ or the radicals R ₄ and R ₅ together with the carbon atoms attached thereto form a benzo ring, wherein R ₄ is additionally-(CH ₂ ) _{if p} -COR ₁₅ or-(CH ₂ ) _q OH or R ₃ , R ₅ and R ₆ are hydrogen, R ₄ is additionally a radical of formula (3),

R ₁₅ is hydroxy, C ₁ -C ₁₂ alkoxy or ego,

R ₁₆ and R ₁₇ are methyl groups or together with the C atoms attached thereto form a C ₅ -C ₈ cycloalkylidene ring which is unsubstituted or substituted one to three times with C ₁ -C ₄ alkyl;

R ₂₄ and R ₂₅ are independently of each other hydrogen or C ₁ -C ₁₂ alkyl,

p is 1 or 2, and

q is 2, 3, 4, 5 or 6.

Of particular interest are compositions comprising as component (b) one or more compounds of formula (1) wherein at least _{two of the} radicals R ₂ , R ₃ , R ₄ and R ₅ are hydrogen.

Of particular interest are compositions comprising as component (b) at least one compound of the formula (1) in which R ₃ and R ₅ are hydrogen.

Very important are compositions comprising as component (b) one or more compounds of formula (1) defined as follows:

R ₂ is C ₁ -C ₄ alkyl,

R ₃ is hydrogen,

R ₄ is C ₁ -C ₄ alkyl, or if R ₆ is hydrogen, R ₄ is additionally a radical of formula (3),

R ₅ is hydrogen, and

R ₁₆ and R ₁₇ together with the C atoms attached to them form cyclohexylidene.

The following compounds are examples of the benzofuran-2-one type which are particularly suitable as component (b) in the novel composition: 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert- Butyl-benzofuran-2-one; 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one; 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2-one]; 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one; 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one; 3- (3,5-dimethyl-4-pivaloyloxy-phenyl) -5,7-di-tert-butyl-benzofuran-2-one; 5,7-di-tert-butyl-3-phenylbenzofuran-2-one; 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) benzofuran-2-one; 5,7-di-tert-butyl-3- (2,3-dimethylphenyl) benzofuran-2-one.

Very important are compositions comprising as component (b) one or more compounds of formula (5):

In the above formula,

R ₂ is hydrogen or C ₁ -C ₆ alkyl,

R ₃ is hydrogen,

R ₄ is hydrogen or C ₁ -C ₆ alkyl,

R ₅ is hydrogen,

R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are independently of each other hydrogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy, provided the radicals R ₇ , R ₈ , R ₉ , R ₁₀ and At least two of R ₁₁ are hydrogen.

Very particular preference is given to compositions comprising as component (b) at least one compound of formula (5a) or (5b) or a mixture of two compounds of formula (5a) and (5b):

Compounds of the benzofuran-2-one type as component (b) in the novel compositions are known in the literature and their preparation is described, for example, in the following US patents: US 4,325,863; US 4,388,244; US 5,175,312; US 5,252,643; US 5,216,052; US 5,369,159; US 5,488,117; US 5,356,966; US 5,367,008; US 5,428,162: US 5,428,177 or US 5,516,920.

Of particular interest are compositions comprising as component (c) at least one compound selected from the group of organic phosphites or phosphonites of the formulas (14) to (20):

In the above formula,

n 'is 2, 3 or 4; p 'is 1 or 2; q 'is 2 or 3; r 'is 4 to 12; y 'is 1, 2 or 3; And z 'is 1 to 6;

A 'is C ₂ -C ₁₈ alkylene when n' is 2; C ₂ -C ₁₂ alkylene comprising oxygen, sulfur or -NR ₄ '-in the middle of the chain; Chemical formula , Radicals or phenylene,

A 'is n' is 3, the formula -C _{r 'H 2r'-1} - radical in which p is 1 to 100;

A 'is equal to 4 if n' is 4 ego;

A '' is the meaning of A 'when n' is 2;

B 'is a direct bond, -CH _2- , -CHR' _4- , -CR ' ₁ R' _4- , sulfur or C ₅ -C ₇ cycloalkylidene, or from 1 to 3, 4 and / or 5 positions Cyclohexylidene substituted by four C ₁ -C ₄ alkyl radicals;

D 'is methyl when p' is 1 and -CH ₂ OCH ₂ -when p 'is 2;

E ′ is C ₁ -C ₁₈ alkyl, —OR ′ ₁ or halogen when y ′ is 1;

E 'is -O-A' '-O- when y' is 2,

E 'is a radical of the formula R ₄ ' C (CH ₂ O-) ₃ or N (CH ₂ CH ₂ O-) ₃ when y 'is 3;

Q 'is at least a radical of the z'-alcohol or phenol, which radical is attached to the phosphorus atom via an oxygen atom;

R ' ₁ , R' ₂ and R ' ₃ are independently unsubstituted or halogen, -COOR ₄ ', -CN- or -CONR ₄ 'R ₄ ' -substituted C ₁ -C ₁₈ alkyl; C ₂ -C ₁₈ alkyl including oxygen, sulfur or —NR ₄ ′-in the middle of the chain; C ₇ -C ₉ phenylalkyl; C ₅ -C ₁₂ cycloalkyl, phenyl or naphthyl; Halogen, naphthyl or phenyl substituted by 1 to 3 alkyl radicals or alkoxy radicals having a total of 1 to 18 carbon atoms or C ₇ -C ₉ phenylalkyl; Or chemical formula Is a radical where m 'is an integer from 3 to 6;

R ' ₄ is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl or C ₇ -C ₉ phenylalkyl,

R ' ₅ and R' ₆ are independently of each other hydrogen, C ₁ -C ₈ alkyl or C ₅ -C ₆ cycloalkyl,

R ' ₇ and R' ₈ are independently of each other C ₁ -C ₄ alkyl when q 'is 2 or together are 2,3-dihydropentamethylene radicals; And

R ' ₇ and R' ₈ are methyl when q 'is 3,

R _'14 is hydrogen, C ₁ -C ₉ alkyl or cyclohexyl,

R _'15 is hydrogen or methyl, radicals R' ₁₄ and R _'15 are present when two or more, and these radicals are identical to or different from each other,

X 'and Y' are each a direct bond or oxygen,

Z 'is a direct bond, methylene, -C (R' ₁₆ ) ₂ -or sulfur, and

R _'16 is C ₁ -C ₈ alkyl.

Of particular interest are compositions comprising as component (c) a phosphite or phosphonite of formula (14), (15), (18) or (19), defined as follows:

n 'is 2 and y' is 1, 2 or 3;

A 'is C ₂ -C ₁₈ alkylene, p-phenylene or p-biphenylene,

E ′ is C ₁ -C ₁₈ alkyl, —OR ′ ₁ or fluorine when y ′ is 1;

E 'is p-biphenylene when y' is 2,

E 'is N (CH ₂ CH ₂ O-) ₃ when y' is 3;

R ' ₁ , R' ₂ and R ' ₃ are independently of each other C ₁ -C ₁₈ alkyl, C ₇ -C ₉ phenylalkyl, cyclohexyl, phenyl or 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms Phenyl substituted by;

R _'14 is hydrogen or C ₁ -C ₉ alkyl,

R _'15 is hydrogen or methyl,

X 'is a direct bond,

Y 'is oxygen,

Z 'is a direct bond or -CH (R' ₁₆ )-, and

R _'16 is C ₁ -C ₄ alkyl.

Of further interest is a composition comprising as component (c) a phosphite or phosphonite of formula (14), (15), (18) or (19), defined as follows:

n 'is 2 and y' is 1 or 3;

A 'is p-biphenylene,

E ′ is C ₁ -C ₁₈ alkoxy or fluorine when y ′ is 1;

E 'is N (CH ₂ CH ₂ O-) ₃ when y' is 3;

R ' ₁ , R' ₂ and R ' ₃ are independently of each other C ₁ -C ₁₈ alkyl or phenyl substituted by 2 to 3 alkyl radicals having a total of 2 to 12 carbon atoms;

R _'14 is hydrogen or tert-butyl;

R _'15 is hydrogen;

X 'is a direct bond;

Y 'is oxygen; And

Z 'is a direct bond, methylene or -CH (CH ₃ )-.

Especially preferred are compositions comprising as component (c) phosphites or phosphonites of formula (14), (15) or (19).

Especially preferred are compositions comprising as component (c) one or more compounds of formula (7):

In the above formula,

R ₁ and R ₂ are independently of each other hydrogen, C ₁ -C ₈ alkyl, cyclohexyl or phenyl, and

R ₃ and R ₄ are independently of each other hydrogen or C ₁ -C ₄ alkyl.

The following compounds are examples of organic phosphites and phosphonites which are particularly suitable as component (c) in novel compositions.

Triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2, 4-di-tert-butylphenyl) phosphite (Irgafos ^R 168 Ciba-Geigy), diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite ( Formula (24)), bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (formula (25)), bisisodecyloxy-pentaerythritol diphosphite, bis (2 , 4-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite ^{(Irgafos R PEP-Q, Ciba} -Geigy, chemical (28)), 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo [d, g] -1,3,2-dioxaphosphosine (Formula 23 )), 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenzo [d, g] -1,3,2-dioxaphosphosine (Formula (21)) , Bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite (Formula 27).

Especially preferred are the use of the following phosphites and phosphonites:

Tris (2,4-di-tert-butylphenyl) phosphite (Irgafos ^R 168 Ciba-Geigy), tris (nonylphenyl) phosphite,

Very particular preference is given to tris (2,4-di-tert-butylphenyl) phosphite [Irgafos ^R 168 Ciba Spezialitatenchemie AG], bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite [ Irgafos ^R 38 Ciba Spezialitatenchemie AG, formula (27)], or tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite [Irgafos ^R PEP-Q, Ciba Spezialitatenchemie AG, formula (28)].

The organic phosphites and phosphonites described above are known compounds, many of which are commercially available.

Important compositions include comprising at least one compound of formula (6) as component (d):

In the above formula,

R ₁ is C ₁ -C ₄ alkyl,

n is 1, 2, 3 or 4,

X is methylene, or ego,

Y is oxygen or -NH-; And,

If n is 1,

X is Wherein Y is attached to R ₂ ,

R ₂ is C ₁ -C ₂₅ alkyl; And

if n is 2,

X is Wherein Y is attached to R ₂ , and

R ₂ is C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkylene comprising oxygen or sulfur in the middle of the chain; Or if Y is -NH-, R ₂ is additionally a direct bond; And,

if n is 3,

X is methylene or Wherein the ethylene group is attached to R ₂ , and

R ₂ is ego; And,

if n is 4,

X is Wherein Y is attached to R ₂ , and

R ₂ is C ₄ -C ₁₀ alcantetrayl.

Alkyl having 25 carbon atoms or less is a straight or branched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, secondary-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n -Pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl , 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodec Yarn, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, icosyl or docosyl. Preferred meanings of R ₁ are methyl and tert-butyl. Particularly preferred meaning of R ₂ is C ₁ -C ₂₀ alkyl, in particular C ₁ -C ₁₈ alkyl, for example C ₄ -C ₁₈ alkyl. Particularly preferred meaning of R ₂ is C ₈ -C ₁₈ alkyl, in particular C ₁₄ -C ₁₈ alkyl, for example C ₁₈ alkyl.

C ₂ -C ₁₂ alkylene is a straight or branched chain radical such as ethylene, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene or dodecamethylene. The preferred meaning of R ₂ is, for example, C ₂ -C ₁₀ alkylene, in particular C ₂ -C ₈ alkylene. A particularly preferred meaning of R ₂ is for example, C _4- C ₈ alkylene, especially C ₄ -C ₆ alkylene, for example hexamethylene.

C ₄ -C ₁₂ alkylene comprising oxygen or sulfur in the middle of the chain may comprise one or more, for example, —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 CH _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 —. A preferred definition of R ₂ is, for example, C ₄ -C ₁₀ alkylene comprising oxygen or sulfur in the middle of the chain, in particular C ₄ -C ₈ alkylene comprising oxygen or sulfur in the middle of the chain, for example oxygen in the middle of the chain. Or C ₄ -C ₆ alkylene including sulfur. Particularly preferred meaning of R ₂ is, for example, —CH ₂ CH ₂ —O—CH ₂ CH ₂ —O—CH ₂ CH ₂ — or —CH ₂ CH ₂ —S—CH ₂ CH ₂ —.

Alcantetrayl having 4 to 10 carbon atoms is, for example, (Pentaerythritol),

or to be. Pentaerythritol is preferred.

Component (d) may comprise a mixture of different sterically hindered phenols of formula (6).

Important compositions are those as component (d) comprising one or more compounds of formula (6) wherein n is 1, R ₂ is C ₁ -C ₂₀ alkyl.

Preferred are compositions comprising as component (d) at least one compound of the formula (6) as defined below:

when n is 2,

R ₂ is C ₂ -C ₈ alkylene, C ₄ -C ₈ alkylene comprising oxygen or sulfur in the middle of the chain; Or if Y is -NH-, R ₂ is additionally a direct bond; And,

when n is 4,

R ₂ is C ₄ -C ₈ alcantetrayl.

Preferred are compositions comprising as component (d) at least one compound of the formula (6) as defined below:

R ₁ is methyl or tert-butyl,

n is 1, 2 or 4,

X is ego,

Y is oxygen or -NH-; And,

when n is 1,

R ₂ is C ₁₄ -C ₁₈ alkyl; And,

when n is 2,

R ₂ is C ₄ -C ₆ alkylene, or is a chain containing an oxygen in the intermediate C ₄ -C ₆ alkylene; And

when n is 4,

R ₂ is C ₄ -C ₆ alcantetrayl.

Of further interest is a composition comprising as component (d) at least one compound of formula (6) represented by formulas (6a) to (6h):

Irganox ^R 1098

Irganox ^R 1076

Irganox ^R 1010

Irganox ^R 245

Irganox ^R 259

Irganox ^R 1035

Irganox ^R 3114

Irganox ^R 3125

Irganox ^R 1098, Irganox ^R 1076, Irganox ^R 1010, Irganox ^R 245, Irganox ^R 259, Irganox ^R 3114, Irganox ^R 1035 and Irganox ^R 3125 are protected under the trade names of Ciba Spezialitatenchemie AG.

Preference is given to component (d) as a compound of formula (6a), (6b), (6c) or (6d), in particular one or more compounds of formula (6) represented by (6a), (6b) or (6c) It is a composition containing.

Components (d) and compounds of formula (6) of the novel compositions are known and in some cases are commercially available. Possible methods for the preparation of compounds of formula (6) are described, for example, in US Pat. No. 3,330,859 or 3,960,928.

Important compositions include as component (e) one or more radicals of the formula (12) or (13):

In the above formula,

G is hydrogen or methyl, and

G ₁ and G ₂ are hydrogen, methyl or oxygen together.

Particularly important compositions comprise as component (e) at least one compound selected from the group of sterically hindered amines of the compound lineages of (a ') to (g') comprising at least one radical of formula (12) or (13) It is.

(a ') A compound of formula (12a)

In the above formula,

n is a number from 1 to 4,

G and G ₁ are independently of each other hydrogen or methyl,

G ₁₁ is hydrogen, O, hydroxy, NO, -CH ₂ CN, C ₁ -C ₁₈ alkyl, C ₃ -C ₈ alkenyl, C ₃ -C ₈ alkynyl, C ₇ -C ₁₂ aralkyl, C ₁ -C ₁₈ alkoxy, C ₅ -C ₈ cycloalkoxy, C ₇ -C ₉ phenylalkoxy, C ₁ -C ₈ alkanoyl, C ₃ -C ₅ alkenoyl, C ₁ -C ₁₈ alkanoyloxy, benzyloxy, Is a group of glycidyl or -CH ₂ CH (OH) -Z, wherein G ₁₁ is preferably hydrogen, C ₁ -C ₄ alkyl, allyl, benzyl, acetyl or acryloyl,

Z is hydrogen, methyl or phenyl, and

if n is 1,

G ₁₂ is hydrogen, C ₁ -C ₁₈ alkyl which contains nothing in the middle of the chain or contains one or more oxygen atoms in the middle of the chain, or cyanoethyl, benzyl, glycidyl, aliphatic, cycloaliphatic, Aliphatic, unsaturated or aromatic carboxylic acids, monovalent radicals of carbamic acid or phosphorus-containing acids, or monovalent silyl radicals, preferably aliphatic carboxylic acids having from 2 to 18 carbon atoms, cyclo having from 7 to 15 carbon atoms Aliphatic carboxylic acid, an α, β-unsaturated carboxylic acid having 3 to 5 carbon atoms, or a radical of an aromatic carboxylic acid having 7 to 15 carbon atoms, wherein the carboxylic acid is represented by -COOZ ₁₂ to its aliphatic, cycloaliphatic or aromatic moiety. May be substituted one to three times,

Z ₁₂ is hydrogen, C ₁ -C ₂₀ alkyl, C ₃ -C ₁₂ alkenyl, C ₅ -C ₇ cycloalkyl, phenyl or benzyl, and

if n is 2,

G ₁₂ is a divalent radical of C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, xylylene, aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid Or divalent silyl radicals, preferably aliphatic dicarboxylic acids having 2 to 36 carbon atoms, cycloaliphatic or aromatic dicarboxylic acids having 8 to 14 carbon atoms, aliphatic, cycloaliphatic or aromatic having 8 to 14 carbon atoms Is a radical of dicarbamic acid, wherein the dicarboxylic acid may be substituted 1-2 times by -COOZ ₁₂ in its aliphatic, cycloaliphatic or aromatic residue, and

if n is 3,

G ₁₂ is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, aromatic tricarbamic acid or phosphorus-containing acid, which may be substituted by -COOZ ₁₂ in aliphatic, cycloaliphatic or aromatic, or is a trivalent silyl radical, And,

if n is 4,

G ₁₂ is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

The carboxylic acid radicals in each case include radicals of the formula (—CO) _n R wherein the meaning of n is as described above and the meaning of R is evident from the above.

C ₁ -C ₁₂ alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, secondary-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n -Decyl, n-undecyl or n-dodecyl.

As C ₁ -C ₁₈ alkyl, G ₁₁ and G ₁₂ may be, for example, the groups described above and n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

If G ₁₁ is C ₃ -C ₈ alkenyl, examples are 1-propenyl, allyl, metalyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tertiary -Butyl-2-butenyl.

G ₁₁ as C ₃ -C ₈ alkynyl is preferably propargyl.

G ₁₁ as C ₇ -C ₁₂ aralkyl is phenethyl and especially benzyl.

G ₁₁ as C ₁ -C ₈ alkanoyl is for example formyl, propionyl, butyryl, octanoyl, but is preferably acetyl, especially C ₃ -C ₅ alkenoyl, especially acryloyl.

As monovalent radical of carboxylic acid G ₁₂ is for example acetic acid, caproic acid, stearic acid, acrylic acid, methacrylic acid, benzoic acid or β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid radical .

If G ₁₂ is a monovalent silyl radical, examples thereof include radicals of the _formula- (C _j H _2j ) -Si (Z ') ₂ Z''where j is an integer from 2 to 5 and Z' and Z '' Are independently of each other C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy).

If G ₁₂ is a divalent radical of dicarboxylic acid, examples thereof include malonic acid, succinic acid, glutaric acid, adipic acid, suveric acid, sebacic acid, maleic acid, itaconic acid, phthalic acid, dibutylmalonic acid, dibenzyl Malonic acid, butyl (3,5-di-tert-butyl-4-hydroxybenzyl) malonic acid or bicycloheptenedicarboxylic acid radical.

If G ₁₂ is a trivalent radical of tricarboxylic acid, examples thereof are trimellitic acid, citric acid or nitrilotriacetic acid radicals.

If G ₁₂ is a tetravalent radical of tetracarboxylic acid, the example is a tetravalent radical of butane-1,2,3,4-tetracarboxylic acid or pyromellitic acid.

If G ₁₂ is a divalent radical of a dicarboxylic acid, and examples thereof include hexamethylene a dicarboxylic acid or 2,4-tolylene-dicarboxylic acid radical.

Preference is given to compounds of the formula (12a) in which G is hydrogen, G ₁₁ is hydrogen or methyl, n is 2 and G ₁₂ is a diacyl radical of an aliphatic dicarboxylic acid having 4 to 12 carbon atoms.

Examples of this class of polyalkylpiperidine compounds include:

1) 4-hydroxy-2,2,6,6-tetramethylpiperidine

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 β- (3,5-di-tert-butyl-hydroxyphenyl) propionate

9) di (1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) malate

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-diethylpiperidin-4-yl) sebacate

16) Di (1-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate

17) 1-hydroxy-4-β-cyanoethyloxy-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-pentamethylpiperidin-4-yl) dibutylmalonate

23) Di (1,2,2,6,6-pentamethylpiperidin-4-yl) butyl (3,5-di-tert-butyl-4-hydroxy benzyl) malonate

24) Di (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

25) Di (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-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-tetramethylpyridine)

28) Dimethylbis (2,2,6,6-tetramethylpiperidine-4-oxy) silane

29) Phenyltris (2,2,6,6-tetramethylpiperidine-4-oxy) silane

30) Tris (1-propyl-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.

(b ') A compound of formula (12b):

In the above formula,

n is a number of 1 or 2,

G, G ₁ and G ₁₁ are as defined in (a '),

G ₁₃ is hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₅ hydroxyalkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₈ aralkyl, C ₂ -C ₁₈ alkanoyl, C ₃ -C ₅ Alkenoyl, benzoyl or chemical formula And,

If n is 1,

G ₁₄ is hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₈ alkenyl, C ₅ -C ₇ cycloalkyl, or C ₁ -substituted by hydroxy, cyano, alkoxycarbonyl or carbamide groups C ₄ alkyl; Glycidyl, a group of formula -CH ₂ -CH (OH) -Z or a group of formula -CONH-Z, wherein Z is hydrogen, methyl or phenyl, and

if n is 2,

G ₁₄ is C ₂ -C ₁₂ alkylene, C ₆ -C ₁₂ arylene, xylene, -CH ₂ -CH (OH) -CH ₂ -group or -CH ₂ -CH (OH) -CH ₂ -ODO- ( Wherein D is C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene, C ₆ -C ₁₂ cycloalkylene), or provided that G ₁₃ is not alkanoyl, alkenoyl or benzoyl, and G ₁₄ is 1 May be a divalent radical of an oxo-C ₂ -C ₁₂ alkylene, aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or may be a -CO- group, or

If n is 1,

G ₁₃ and G ₁₄ may together be a divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

C ₁ -C ₁₂ -or C ₁ -C ₁₈ alkyl substituents are as defined above in (a ′).

The C ₅ -C ₇ cycloalkyl substituent is in particular cyclohexyl.

As C ₇ -C ₈ aralkyl G ₁₃ is especially phenylethyl or especially benzyl. G ₁₃ as C ₂ -C ₅ hydroxyalkyl is especially 2-hydroxyethyl or 2-hydroxypropyl.

G ₁₃ as C ₂ -C ₁₈ alkanoyl is for example propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but is preferably acetyl and especially acryl as C ₃ -C ₅ alkenoyl It's Royle.

If G ₁₄ is C ₂ -C ₈ alkenyl, examples are allyl, metalyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

As C ₁ -C ₄ alkyl substituted by hydroxy, cyano, alkoxycarbonyl or carbamide groups G ₁₄ is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbo Carbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2- (dimethylaminocarbonyl) ethyl.

C ₂ -C ₁₂ alkylene substituents are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

C ₆ -C ₁₅ arylene substituents are, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

Especially mentioned above as C ₆ -C ₁₂ cycloalkylene may be cyclohexylene.

Preferred are n is 1 or 2, G is hydrogen, G ₁₁ is hydrogen or methyl, G ₁₃ is hydrogen, C ₁ -C ₁₂ alkyl or a formula And G ₁₄ is hydrogen or C ₁ -C ₁₂ alkyl when n is 1 and C ₂ -C ₈ alkylene or 1-oxo-C ₂ -C ₈ alkylene when n is 2 ) Compound.

Examples of this class of polyalkylpiperidine compounds include:

37) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1,6-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-xylenediamine

44) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) succinamide

45) di (2,2,6,6-tetramethylpiperidin-4-yl) N- (2,2,6,6-tetramethylpiperidin-4-yl) -β-aminopropionate

46) Chemical formula Compound of

47) 4- (bis-2-hydroxyethylamino) -1,2,2,6,6-pentamethylpiperidine

48) 4- (3-methyl-4-hydroxy-5-tert-butylbenzamido) -2,2,6,6-tetramethylpiperidine

49) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine

(c ') A compound of formula (12c):

In the above formula,

n is 1 or 2, G, G ₁ and G ₁₁ are as defined above in (a '), and

If n is 1,

G ₁₅ is C ₂ -C ₈ alkylene or C ₂ -C ₈ hydroxyalkylene or C ₄ -C ₂₂ acyloxyalkylene, and

if n is 2,

G ₁₅ is (-CH ₂ ) ₂ C (CH _2- ) ₂ .

If G ₁₅ is C ₂ -C ₈ alkylene or C ₂ -C ₈ hydroxyalkylene, examples thereof include ethylene, 1-methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene to be.

G ₁₅ as C ₄ -C ₂₂ acyloxyalkylene is for example 2-ethyl-acetoxymethylpropylene.

Examples of this class of polyalkylpiperidine compounds include:

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] undecane

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 ') Compounds of formulas (12d), (12e) and (12f), preferably compounds of formula (12f):

In the above formula,

n is 1 or 2, G, G ₁ and G ₁₁ are as defined in (a '),

G ₁₆ is hydrogen, C ₁ -C ₁₂ alkyl, allyl, benzyl, glycidyl or C ₂ -C ₆ alkoxyalkyl, and

If n is 1,

G ₁₇ is hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₅ alkenyl, C ₇ -C ₉ aralkyl, C ₅ -C ₇ cycloalkyl, C ₂ -C ₄ hydroxyalkyl, C ₂ -C ₆ Alkoxyalkyl, C ₆ -C ₁₀ aryl, glycidyl or a formula-(CH ₂ ) _p -COO-Q or a formula-(CH ₂ ) _p -O-CO-Q group wherein p is 1 or 2, Q Is C ₁ -C ₄ alkyl or phenyl), and

if n is 2,

G ₁₇ is C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₆ -C ₁₂ arylene, -CH ₂ -CH (OH) -CH ₂ -ODO-CH ₂ -CH (OH) -CH _2- (where D is C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene, C ₆ -C ₁₂ alkylene) group or -CH ₂ CH (OZ ') CH _2- (OCH ₂ -CH (OZ ') CH ₂ ) _2- , wherein Z' is hydrogen, C ₁ -C ₁₈ alkyl, allyl, benzyl, C ₂ -C ₁₂ alkanoyl or benzoyl),

T ₁ and T ₂ independently of one another are hydrogen, C ₁ -C ₁₈ alkyl or unsubstituted or halo- or C ₁ -C ₄ alkyl-substituted C ₆ -C ₁₀ aryl or C ₇ -C ₉ aralkyl, or T ₁ and T ₂ together with the carbon atoms attached to them form a C ₅ -C ₁₄ cycloalkane ring.

C ₁ -C ₁₂ alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, secondary-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n -Decyl, n-undecyl or n-dodecyl.

Substituents in the meaning of C ₁ -C ₁₈ alkyl may be, for example, the groups described above, such as n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

C ₂ -C ₆ alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl Isopropoxyethyl or propoxypropyl.

If G ₁₇ is C ₃ -C ₅ alkenyl, examples are 1-propenyl, allyl, metalyl, 2-butenyl or 2-pentenyl.

As C ₇ -C ₉ aralkyl G ₁₇ , T ₁ and T ₂ are especially phenethyl or especially benzyl. If T ₁ and T ₂ together with the carbon atom form a cycloalkane ring, examples may be cyclopentane, cyclohexane, cyclooctane or cyclododecane rings.

If G ₁₇ is C ₂ -C ₄ hydroxyalkyl, examples thereof are 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

As C ₆ -C ₁₀ aryl G ₁₇ , T ₁ and T ₂ are in particular α- or β-naphthyl substituted by phenyl, unsubstituted or halogen or C ₁ -C ₄ alkyl.

If G ₁₇ is C ₂ -C ₁₂ alkylene, examples thereof are ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

G ₁₇ as C ₄ -C ₁₂ alkenylene is especially 2-butenylene, 2-pentenylene or 3-hexenylene.

If G ₁₇ is C ₆ -C ₁₂ arylene, examples are o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

If Z 'is C ₂ -C ₁₂ alkanoyl, examples thereof are propionyl, butyryl, octanoyl, dodecanoyl, and preferably acetyl.

As C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene or C ₆ -C ₁₂ cycloalkylene, D is as defined in (b ′).

Examples of this class of polyalkylpiperidine compounds include:

56) 3-benzyl-1,3,8-tria-7-7,7,9,9-tetramethylspiro [4.5] decane-2,4-dione

57) 3-n-octyl-1,3,8-tria-7-7,7,9,9-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-tria-7-7,7,8,9,9-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-tetramethyl-1-oxa-3,8-diaza-4-oxospyro [4.5] decane

62) 2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxodisspiro [4.5] decane

63) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodisspiro [5.1.11.2] henic acid

64) 2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxospyro [4.5] decane and preferably:

65) 8-acetyl-3-dodecyl-1,3,8-tria-7-7,7,9,9-tetramethylspiro [4.5] decane-2,4-dione

Or a compound of formula

66)

67)

68)

69)

(e ') Similarly preferred compounds of formula (12 g):

In the above formula,

n is a number of 1 or 2, G ₁₈ is a chemical formula or ego,

Wherein G and G ₁₁ are as defined in (a '),

G ₁ and G ₂ are hydrogen, methyl or together substituent = 0;

E is -O- or -NG _13- ,

A is C ₂ -C ₆ alkylene or-(CH ₂ ) ₃ -O-,

x is a number of 0 or 1,

G ₁₃ is hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₅ hydroxyalkyl or C ₅ -C ₇ cycloalkyl,

G ₁₉ is the same as G ₁₈ or is one of -NG ₂₁ G ₂₂ , -OG ₂₃ , -NHCH ₂ OG ₂₃ or -N (CH ₂ OG ₂₃ ) ₂ ,

G ₂₀ is equal to G ₁₈ or G ₁₉ when n = 1, and when n = 2, G ₂₀ is an -EBE- group where B is C ₂ -C ₈ alkylene or 1 or 2 -N in the middle of the chain C ₂ -C ₈ alkylene containing (G ₂₁ ) -group,

G ₂₁ is C ₁ -C ₁₂ alkyl, cyclohexyl, benzyl or C ₁ -C ₄ hydroxyalkyl or is of the formula Groups or formulas of Is the flag of,

G ₂₂ is C ₁ -C ₁₂ alkyl, cyclohexyl, benzyl or C ₁ -C ₄ hydroxyalkyl, or G ₂₁ and G ₂₂ together are C ₄ -C ₅ alkylene or C ₄ -C ₅ oxaalkylene, For example, —CH ₂ CH ₂ OCH ₂ CH ₂ — or a group of the formula —CH ₂ CH ₂ N (G ₁₁ ) CH ₂ CH ₂ —, and

G ₂₃ is hydrogen, C ₁ -C ₁₂ alkyl or phenyl.

C ₁ -C ₁₂ alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, secondary-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n -Decyl, n-undecyl or n-dodecyl.

C ₂ -C ₅ hydroxyalkyl substituents are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

If A is C ₂ -C ₆ alkylene, examples are ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.

If G ₂₁ and G ₂₂ together are C ₄ -C ₅ alkylene or oxaalkylene, examples are tetramethylene, pentamethylene or 3-oxapentamethylene.

Examples of polyalkylpiperidine compounds of this class include:

70)

71)

72)

73)

74)

75)

Wherein R is the same meaning as in compound 74).

76)

77)

Wherein R 'has the same meaning as in compound 76).

78)

79)

80)

(f ') structural repeat units are 2,2,6,6-tetraalkylpiperidine radicals, in particular polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly (meth ) Acrylates, oligomeric or polymeric compounds containing poly (meth) acrylamides and copolymers thereof comprising these radicals.

Examples of 2,2,6,6-polyalkylpiperidine compounds of this class are compounds of the formula wherein m is a number from 2 to about 200:

81)

82)

83)

84)

85)

86)

87)

88)

89)

90)

91)

92)

93)

94)

95)

Wherein R is Radical or chain And m 'and m''are integers ranging from 0 to 200, provided that m' + m '= m.

Another example of a polymeric compound is Reaction products of epiclohydrin with a compound of; A carboxyl side chain derived from butane-1,2,3,4-tetracarboxylic acid and tetracarboxylic acid is esterified with 2,2,6,6-tetramethyl-4-hydroxypiperidine Polyesters of difunctional alcohols; Chemical formula Of compounds wherein about one third of the radicals R are -C ₂ H ₅ , and the remaining two thirds And m is an integer ranging from 2 to 200; Or repeat units Two units, one And another one A copolymer composed of units.

(g ') A compound of formula (13a):

In the above formula,

n is a number of 1 or 2, G and G ₁₁ are as defined in (a '), G ₁₄ is as defined in (b'), -CONH-Z and -CH ₂ -CH (OH) The meaning of —CH ₂ —ODO— excludes G ₁₄ .

Examples of such compounds are as follows:

100)

101)

102)

Particularly important compositions are those comprising as component (e) at least one compound of the formulas (28a), (28b), (28c), (28d), (28e), (28f) and (28g):

Tinuvin ^R 123

Tinuvin ^R 144

Tinuvin ^R 292

Tinuvin ^R 622

Chimassorb ^R 944

Chimassorb ^R 119

In the above formula,

m is an integer ranging from 2 to 200.

Component (e) or sterically hindered amine type compounds of the novel compositions are known and some are commercially available.

Tinuvin ^R 123, Tinuvin ^R 144, Tinuvin ^R 292, Tinuvin ^R 622, Chimassorb ^R 944 and Chimassorb ^R 119 are protected under the trade names of Ciba Spezialitatenchemie AG.

Particularly preferred as component (e) of the novel composition is the addition of sterically hindered amines having a molecular weight or average molecular weight M _n in the range of 500 to 10 000, in particular in the range of 1000 to 10 000. Of particular importance among these are sterically hindered amines whose molecular weight or average molecular weight M _n is in the range from 1500 to 10 000, for example in the range from 2000 to 7500.

Of particular interest are novel compositions comprising as component (e) two or more sterically hindered amine compounds.

Mixtures of components (b), (c), (d) and (e) are suitable for organic materials stabilized against oxidation, heat or photo-induced decomposition. Examples of such materials are as follows:

1. Polymers of monoolefins and diolefins (such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1ene, polyisoprene or polybutadiene) as well as cycloolefins (such as cyclopentene Or norbornene), optionally crosslinked polyethylene, such as high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene ( MDPE), low density polyethylene (LDPE), straight chain low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

The polymers of polyolefins, ie monoolefins exemplified above, preferably polyethylene and polypropylene, can be prepared in different ways and in particular in the following way:

a) radical reaction (typically at high pressure and elevated temperature).

b) Catalytic reaction using a catalyst which usually contains one or more than one of the IVb, Vb, VIb or Group VIII metals of the periodic table. The metals usually have one or more than one ligand, which can bind π- or σ-coordination such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls. The metal complex may be in free form or immobilized on a substrate such as active magnesium chloride, titanium (III) chloride, alumina or silicon oxide. The catalyst may be soluble or insoluble in the polymerization reaction medium. The catalyst may be used alone in the polymerization process or other activators such as metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, the metals being groups Ia, IIa and IIIa of the periodic table. Is an element of. The activator can be advantageously modified by other ester, ether, amine or silyl ether groups. The catalyst system is commonly named Philips, standard oil Indiana, Ziegler (-Natta), TNZ (Dupont), metallocene or single site catalyst (SSC).

2. Mixtures of the polymers described in 1), such as polypropylene and polyisobutylene, polypropylene and polyethylene (such as PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (eg LPDE / HDPE).

3. Copolymers of monoolefin and diolefins with one another or with other vinyl monomers, such as ethylene / propylene copolymers, straight chain low density propylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / but-1-ene air Copolymer, propylene / isobutylene copolymer, ethylene / but-1-ene copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, propylene / butadiene copolymer Isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers and copolymers thereof with carbon monoxide or ethylene / acrylic acid copolymers and salts thereof (Ionomer) as well as ethylene with propylene and dienes (such as hexadiene, dicyclopentadiene or ethylidene-norbornene) coalescence; And mixtures of the copolymers with each other or with the polymers described above in 1), such as polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and cross or random polyalkylene / carbon monoxide copolymers and mixtures of these with other polymers such as polyamides.

4. Hydrocarbon resins (such as C ₅ -C ₉ ) and mixtures of polyalkylenes and starches, including hydrogenation modifiers (such as tackifier resins).

5. Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene).

6. For example styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl Styrene such as acrylate or a copolymer of α-methylstyrene with diene or acrylic acid derivatives; High impact strength mixtures consisting of styrene copolymers and other polymers such as polyacrylates, diene polymers or ethylene / propylene / diene trimers; And block copolymers of styrene such as, for example, styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

7. styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymer, styrene on polybutadiene and acrylonitrile (or methacrylonitrile); Styrene, acrylonitrile and methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene, styrene and maleic acid on polybutadiene; Styrene and alkyl acrylates or methacrylates on polybutadiene; Styrene and acrylonitrile on ethylene / propylene / diene trimers; 6) Graft copolymers of styrene or a-methylstyrene, such as styrene and acrylonitrile on polyalkylacrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate / butadiene copolymers Mixtures of listed copolymers (eg copolymer mixtures known as ABS, MBS, ASA or AES polymers).

8. chlorinated or brominated copolymers of polychloroprene, chlorinated rubber, isobutyrene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, In particular halogen-containing polymers such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as polymers of halogen-containing vinyl compounds, for example vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate Or copolymers thereof such as vinylidene chloride / vinyl acetate copolymer.

9. polymers derived from α, β-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; Polymethyl methacrylate, polyacrylamide and polyacrylonitrile impact-modified with butyl acrylate.

10. Copolymers between monomers described above in 9) or between other unsaturated monomers. For example acrylonitrile / butadiene copolymer, acrylonitrile / alkyl acrylate copolymer, acrylonitrile / alkoxyalkyl acrylate copolymer or acrylonitrile / vinyl halide copolymer or acrylonitrile / alkyl methacrylate / butadiene 3 coalescence.

11. From unsaturated alcohols such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate or polyvinyl maleate, polyvinylbutyral, polyallyl phthalate or polyallyl melamine and amines or acyl derivatives thereof Derived polymers; As well as the olefins and copolymers thereof described above in 1).

12. Homogeneous polymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxides, polypropylene oxides or copolymers thereof with bisglycidyl ethers.

13. polyacetals such as polyoxymethylene and polyoxymethylene containing for example ethylene oxide as comonomers; Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.

15. Polyurethanes derived from polyethers, polyesters or polybutadienes with hydroxyl groups at one end and aliphatic or aromatic polyisocyanates at the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6 / Aromatic polyamides derived from 12, 4/6, 12/12, polyamide 11, polyamide 12, m-xylene diamine and adipic acid; Hexamethylene diamine and isophthalic acid or / and terephthalic acid and, optionally, as a modifier, for example polys made from elastomers such as poly-2,4,4-trimethylhexamethylene terephthalamide, poly-m-phenyleneisophthalamide amides; Block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or branched elastomers; Or block copolymers with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; As well as polyamides or copolyamides modified with EPDM or ABS; And polyamides condensed during processing (reactant injection molding (RIM) polyamide systems).

17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.

18. Polyesters derived from dicarboxylic and diols and / or hydroxycarboxylic acids such as, for example, polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylol-cyclohexane terephthalate and polyhydroxybenzoate or Block-copolyether esters derived from polyethers having hydroxy end groups as well as the corresponding lactones; And polyesters modified with polycarbonates or MBS.

19. Polycarbonates and Polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on one side and phenols, ureas and melamine on the other, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.

22. Dry and undry alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds and their low-flammability, crosslinking agents.

24. Crosslinkable acrylic resins derived from substituted acrylates such as epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, such as bisphenol A and bisphenol F, crosslinked with conventional curing agents such as anhydrides or amines without linkages or accelerators with accelerators. Product of diglycidyl ether.

27. Natural polymers such as cellulose, rubber, gelatin and chemically modified cognate derivatives thereof such as cellulose acetate, cellulose propionate and cellulose ethers such as cellulose butyrate or methyl cellulose; As well as rosin and derivatives thereof.

28. Mixtures of the aforementioned polymers (composites), such as PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

29. Natural and synthetic organic materials that are pure monomer compounds or mixtures of these compounds, such as mineral oils, animal and vegetable fats, oils and waxes, or synthetic esters (eg phthalates, adipates, phosphates or trimellitates) and various weight ratios Fats and waxes based on mixtures of mineral oils with synthetic esters, such as materials used in spinning compositions, as well as aqueous emulsions of these materials.

30. Aqueous emulsions of natural or synthetic rubbers, such as natural latices or latices of carboxylated styrene / butadiene copolymers.

Mixtures of components (b), (c), (d) and (e) are used for the production of polyurethanes, in particular for the production of flexible polyurethane foams. In this regard the novel compositions and products resulting from them are effectively protected against degradation. It prevents scorching, especially during foam manufacture.

Polyurethanes are obtained, for example, by reacting polyethers, polyesters and polybutadienes containing terminal hydroxy groups with aliphatic or aromatic polyisocyanates.

Polyethers containing terminal hydroxy groups are known and are for example polymerized with epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin, for example by polymerizing with each other in the presence of BF _3. Or these epoxides, alone or as a mixture or in succession, from a reactive hydrogen atom-containing starting component such as water, alcohol, ammonia or amines such as ethylene glycol, propylene, 1,3- and 1,2-glycol, It is prepared by addition reaction with trimetholpropane, 4,4'-dihydroxydiphenylpropane, aniline, ethanolamine or ethylenediamine. Sucrose polyethers are suitable for the present invention. Preferred in many cases are polyethers which predominantly contain predominantly OH groups (up to 90% by weight based on all OH groups present in the polyether). In addition, polyethers modified with vinyl polymers, for example as formed by polymerizing styrene and acrylonitrile in the presence of polyethers, are as suitable as polybutadiene containing OH groups.

These compounds generally have a molecular weight of 400 to 10000 and are polyhydroxy compounds, especially compounds containing 2 to 8 hydroxy groups, especially those having a molecular weight of 800 to 10 000, preferably 1000 to 6000, for example at least two And generally 2 to 8, but preferably 2 to 4, hydroxy groups, each of which is known for producing uniform polyurethanes and porous polyurethanes.

It is also applicable to mixtures of the above-mentioned compounds which contain two or more isocyanate-active hydrogen atoms, especially those having a molecular weight of 400-10 000.

Suitable polyisocyanates include aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates such as ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate Isocyanate, cyclobutane 1,3-diisocyanate, cyclohexane 1,3- and -1,4-diisocyanate and desired mixtures of these isomers, 1-diisocyanato-3,3,5-trimethyl-5- Isocyanatomethylcyclohexane, 2,4- and 2,6-hexahydrotolylene diisocyanate and desired mixtures of these isomers, hexahydro-1,3- and / or -1,4-phenylene diisocyanate , Perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene di Isocyanates and desired mixtures of these isomers, diphenylme Tan 2,4'- and / or -4,4'-diisocyanate, naphthylene 1,5-diisocyanate, triphenylmethane 4,4 ', 4' '-triisocyanate, polyphenyl-polymethylene polyisocyanate These are obtained by aniline-formaldehyde condensation reaction according to phosgenation, m- and p-isocyanatophenylsulfonyl isocyanate, perchlorinated aryl polyisocyanate, carbodiimide group-containing polyisocyanate, allophanate group-containing Polyisocyanates, polyisocyanates containing isocyanurate groups, polyisocyanates containing urethane groups, polyisocyanates containing acylated urea groups, polyisocyanates containing biuret groups, polyisocyanates containing ester groups, reaction products of the above-mentioned isocyanates and acetals and polymer fatty acid radicals Containing polyisocyanate.

It is also possible to apply distillation residue containing-isocyanates, which may be or be dissolved in one or more of the aforementioned polyisocyanates and are obtained by industrial preparation of isocyanates. It may additionally be used in the desired mixture of the isocyanates described above.

Particular preference is given to polyisocyanates which can generally be obtained industrially, for example 2,4- and 2,6-tolylene diisocyanate and the desired mixtures of these isomers ("TDI"), polyphenyl-polymethylene-poly Isocyanates, which are obtained by aniline-formaldehyde condensation reactions following phosgenation (“crude MDI”), and polyisocyanates containing carbodiimides, urethanes, allophanates, isocyanurates, ureas or biuret groups (“ Modified polyisocyanate ").

The organic material to be protected is preferably a natural, semisynthetic or preferably synthetic polymer. Especially preferred are thermoset polymers, in particular polyolefins, in particular polyethylene and polypropylene or mono- and di-olefins and copolymers thereof.

Of particular importance is the action of the new composition on heat and oxidative degradation, in particular under thermal stresses generated during the processing of thermosets. The new components (b), (c), (d) and (e) are therefore excellently suited for use in processing (in processing) stabilizers.

Mixtures of components (b), (c), (d) and (e) are suitable for stabilizing polyolefins in prolonged contact with the extraction medium.

Component (b) is preferably added at 0.0005 to 5%, in particular 0.001 to 2%, such as 0.01 to 2%, based on the weight of the organic material to be stabilized.

Components (c), (d) and (e) are based on the organic material to be stabilized, based on the weight of the organic material to be stabilized, for example from 0.01 to 10%, for example from 0.01 to 5%, preferably from 0.025 to 3% and especially from 0.025 to Carefully added at 1%.

In adding the components (a), (b), (c), (d) and (e), the new composition may further comprise the following co-stabilizers (additives):

1. Antioxidant

1.1. Alkylated monophenols such as 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-isobutylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (α- Methylcyclohexyl) -4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth Oxymethylphenol, nonylphenol branched into straight or branched chains such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundes-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) phenol and mixtures thereof.

1.2. Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-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-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxy Anisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

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

1.5. Hydroxylated thiodiphenyl ethers such as 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'-thiobis- (3,6-di-secondary Amylphenol), 4,4'-bis- (2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidenebisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'- Methylenebis [4-methyl-6- (α-methylcyclohexyl) -phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl 4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2, 2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-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-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydrate 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-dodecylmer Tobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopenta Diene, 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 Oxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 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, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl 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, isooctyl-3 , 5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates such as 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-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.

1.9. Aromatic hydroxybenzyl compounds such as 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, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.

1.10. Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmer Capto-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-tertiary -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, 1,3,5- 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, di Octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, 3,5-di Calcium salt of monoethyl ester of tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.

1.13. Mono or polyhydric alcohols such as 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-thiaundanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and β- (3,5- Esters of di-tert-butyl-4-hydroxyphenyl) propionic acid.

1.14. Mono or polyhydric alcohols such as 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) oxaamide, 3-thiaundanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and β- (5-tertiary- Esters of butyl-4-hydroxy-3-methylphenyl) propionic acid .

1.15. Monohydric or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundanol, 3-thiapentadecanol, Trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and β- (3,5-dicyclohexyl-4-hydrate Esters of oxyphenyl) propionic acid .

1.16. Monohydric or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundanol, 3-thiapentadecanol, Trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and 3,5-di-tert-butyl-4-hydroxy Esters of phenyl acetic acid .

1.17. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid , such as N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexa Methylenediamine, 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'-di-isopropyl-p-phenylenediamine, N, N'-di-secondary-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethyl Pentyl) -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'-bis (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-toluenesulfamoyl) -diphenylamine, N, N'-dimethyl-N, N'-di -Secondary-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl ) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine such as p, p'-di-tert-octyldiphenylamine, 4-n-butyl Minophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di- Tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4' -Diaminodiphenylmethane, 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, mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamine, mono- and dialkylated nonyldiphenyl Mixtures of amines, mixtures of mono- and dialkylated dodecyldiphenylamines, mixtures of mono- and dialkylated isopropyl / isohexyldiphenylamines, mixtures of mono- and dialkylated tert-butyldiphenylamines, 2,3- Dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, parent And mixtures of dialkylated tert-butyl / tert-octylphenothiazine, mixtures of mono- and dialkylated tert-octyl-phenothiazine, N-allylphenothiazine, N, N, N ', N'-tetra Phenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethyl-piperidin-4-yl-hexamethylenediamine, bis (2,2,6 , 6-tetramethylpiperid-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol .

2. UV absorbers and light stabilizers.

2.1. 2- (2'-hydroxyphenyl) benzotriazole such as 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-chloro-benzotriazole, 2- (3'-tertiary -Butyl-2'-hydroxy-5'-methylphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole , 2- (2'-hydroxy-4'-octyloxyphenyl) 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-chloro-benzotria, 2 '-(3'-tert-butyl-5'-[2- (2-ethylhexyloxy) -carbonylethyl] -2 ' -Hydroxyphenyl) -5-chloro-benzo Riazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert- Butyl-2'-hydroxy-5 '-(2-methoxycarbonyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarb Carbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2 -(3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonyl Ethyl) phenylbenzotriazole, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; 2- [3'- Tert-butyl-5 '-(2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole and a transesterification product of polyethylene glycol 300; [R-CH ₂ CH _2- COO- CH ₂ CH _2- ] ₂ (R is 3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl), 2- [2′-hydroxy-3 ′ -( , α-dimethylbenzyl) -5 '-(1,1,3,3-tetramethylbenzyl) -phenyl] benzotriazole, 2- [2'-hydroxy-3'-(1,1,3,3 -Tetramethylbenzyl) -5 '-(α, α-dimethylbenzyl) -phenyl] benzotriazole.

2,2, 2-hydroxybenzophenones such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4 '-Trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of unsubstituted or substituted benzoic acids such as 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butyl-benzoyl) resorci Nol, Benzoyl Resorcinol, 2,4-Di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxy Benzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxy Benzoate.

2.4. Acrylates such as ethyl α-cyano-β, β-diphenylacrylate, isooctyl α-cyano-β, β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano- β-methyl-p-methoxy-cinnamate, butyl α-cyano-β-methyl-p-methoxy-cinnamate, methyl α-carbomethoxy-p-methoxy-cinnamate and N- (β- Carbomethoxy-β-cyanovinyl) -2-methylindolin.

2.5 2,2'-thio-bis [4- (1,1,3,3- with optionally ligands such as n-butylamine, triethanolamine or N-cyclohexyl diethanolamine Tetramethylbutyl) phenol] nickel complex (such as 1: 1 or 1: 2 complex), nickel dibutyl dithiocarbamate, monoalkyl of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid Nickel salts of esters (such as methyl esters or ethyl esters), nickel complexes of ketoximes (such as 2-hydroxy-4-methylphenyl undecylketoxime), 1-phenyl-4-lauroyl, optionally with additional ligands Nickel complex of -5-hydroxypyrazole.

2.6. Sterically hindered amines such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate, 1- (2-hydroxy Condensation product of ethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl Linear or cyclic condensation products of hexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethyl-4-pi Ferridyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate, 1,1 '-(1 , 2-ethanediyl) -bis- (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetra Tilpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2 -(2-hydroxy-3,5-di-tert-butylbenzyl) 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-tetramethylpi Ferridyl) succinate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3, Linear or cyclic condensation products of 5-triazines, 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5- Condensation product of triazine with 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-pi Ridyl) pyrrolidine-2,5-dione, 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N, N'-bis- ( Condensation product of 2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine with 4-cyclohexylamino-2,6-di-chloro-1,3,5-triazine, 1, 4-butylamino-2,2,6,6-tetramethylpiperidine as well as 2-bis- (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine Condensation products of (CAS Reg. No. [136504-96-6]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-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-4-oxospyro [4,5] decane with epichlorohydrin, product 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, 4-methoxy-methylene-malonic acid and 1,2,2,6,6-pentamethyl-4-hydroxypi Diesters of ferridine, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, maleic anhydride-α-olefin-copolymer Reaction product of 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamides such as 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanide, 2 , 2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide , 2-ethoxy-5-tert-butyl-2'-ethoxanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and o- and mixtures of p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.

2.8. 2- (2-hydroxyphenyl) -1,3,5-triazine such as 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-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-butoxy-propoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl]- 4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxy- Nil] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxy-propoxy ) Phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl- 1,3,5-triazine, 2- (2-hydroxy-4-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, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] phenyl} -4, 6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

3. Metal deactivators such as N, N'-diphenyloxamide, N-salicyl-N'-salicyloyl 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, oxanyl Reed, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N, N'-diacetyladifoyl dihydrazide, N, N'-bis (salicyloyl) oxalyl dihydrazide, N, N ' Bis (salicyloyl) thiopropionyl dihydrazide.

4. Phosphites and phosphonites such as triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl Pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaeryte Ritol diphosphite, bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4 '-Biphenylene diphosphonite, 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-dioxaphosphosine, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl -6-methylphenyl) ethylphosphite, 2,2 ', 2''-nitrilo [triethyltris (3,3'5,5'-tetra-tert-butyl-1,1'-biphenyl-2 , 2'-diyl) phosphite], 2-ethylhexyl (3,3'5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite.

5. Hydroxyamines such as N, N-dibenzylhydroxyamine, N, N-diethylhydroxyamine, N, N-dioctylhydroxyamine, N, N-dilaurylhydroxyamine, N, N Ditetradecylhydroxyamine, N, N-dihexadecylhydroxyamine, N, N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl-N- Octadecylhydroxyamine, N, N-dialkylhydroxyamine derived from hydrogenated resin amine.

6. Nitrons such as N-benzyl-alpha-phenyl-nitron, N-ethyl-alpha-methyl-nitron, N-octyl-alpha-heptyl-nitron, N-lauryl-alpha-undecyl-nit Ron, N-tetradecyl-alpha-tridecyl-nitron, N-hexadecyl-alpha-pentadecyl-nitron, N-octadecyl-alpha-heptadecyl-nitron, N-hexadecyl-alpha-heptadecyl -Nitron, N-octadecyl-alpha-pentadecyl-nitron, N-heptadecyl-alpha-heptadecyl-nitron, N-octadecyl-alpha-hexadecyl-nitron, N derived from hydrogenated resin amine Nitron derived from, N'-dialkylhydroxyamine.

7. Thio synergists , such as dilauryl thiodipropionate or distearyl thiodipropionate.

8. Peroxide decomposers such as esters of β-thiodipropionic acid, such as lauryl, stearyl, myristyl or tridecyl esters, zinc salts of mercaptobenzimidazole or 2-mercaptobenzimidazole, dibutyldithio Zinc carbamate, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecylmercapto) propionate.

9.Polyamide stabilizers such as copper salts and divalent magnesium salts in combination with iodides and / or phosphorus compounds.

10. Basic co-stabilizers such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of high fatty acids, Such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatechol or tin pyrocatechol.

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

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

13. Other additives such as plasticizers, lubricants, emulsifiers, pigments, flow additives, catalysts, flow-controlling agents, optical brighteners, flame retardants, antistatic agents and blowing agents.

Co-stabilizers are added at concentrations of from 0.01 to 10%, for example based on the total weight of organic material to be stabilized.

Fillers and reinforcing agents (as detailed in claim 12) For example, talc, calcium carbonate, mica or kaolin is added to the polyolefin at a concentration of from 0.01 to 40%, for example based on the total weight of the polyolefin being stabilized.

Fillers and reinforcing agents (as detailed in claim 12) For example, metal hydroxides, in particular aluminum hydroxide or magnesium hydroxide, are added to the polyolefin at a concentration of from 0.01 to 60%, for example based on the total weight of the polyolefin to be stabilized.

Carbon black as filler is carefully added to the polyolefin at a concentration of 0.01 to 5% based on the total weight of the polyolefin to be stabilized.

Glass fibers as reinforcing agent are carefully added to the polyolefin at a concentration of 0.01 to 20% based on the total weight of the polyolefin to be stabilized.

Other preferred compositions include in addition to components (a) to (e), as well as other additives, in particular alkaline earth metal salts of higher fatty acids, such as calcium stearate.

As a conventional stabilizer formulation for processing polyolefins for producing moldings, for example, a combination of a secondary antioxidant and phenolic antioxidant based on organic phosphites or phosphonites is recommended. However, depending on the particular substrate and processing, many polyolefin manufacturers will process in the high temperature range above about 280 ° C. Industrial materials and moldings based on high-density polyethylene, for example by incorporating novel processing stabilizer mixtures of components (b), (c), (d) and (e) suitable for applications at high temperatures, in particular at least 300 ° C Pipes and their technical modifications (fittings) can be produced at higher speeds and at lower failure rates. Another advantage of this stabilizer mixture is that it is available in very small amounts. This reduces the overall concentration of antioxidants relative to conventional stabilizer mixtures. Therefore, the use of a low concentration of the benzofuran-2-one type [component (b)] stabilizer reduces the overall concentration of the stabilizer by about one third in the polyolefin and at the same time provides an economic advantage.

The incorporation of components (b), (c), (d) and (e) and the desired other additives into the polymeric organic material is carried out by known methods, for example, dissolved or dispersed stable to shaped or polymeric organic materials. Before and after application of the agent mixture, if necessary, the solvent is then evaporated. If desired, other additives and stabilizer mixtures of components (b), (c), (d) and (e) may be stabilized in the form of a masterbatch containing these components, for example at a concentration of 2.5 to 25% by weight. Can be added to.

Stabilizer mixtures of components (b), (c), (d) and (e) with or without other additives may be added before or during the polymerization or before the crosslinking reaction.

Stabilizer mixtures of components (b), (c), (d) and (e) with or without other additives may be encapsulated in pure form or in polymers of waxes, oils or stabilized organic materials.

Stabilizer mixtures of components (b), (c), (d) and (e) with or without other additives may be sprayed onto the polymer to be stabilized. They may be sprayed on polymers which are diluted with other additives (such as the conventional additives described above) or their melts to stabilize with these additives. The addition by spraying during the deactivation of the polymerization catalyst is particularly advantageous since it can be sprayed using, for example, the steam used for deactivation.

In the case of spherical polymerized polyolefins, it may be advantageous, for example, as applied by spraying together with or without the addition of stabilizer mixtures of components (b), (c), (d) and (e).

The materials to be stabilized in this way can be used in various forms, for example as binders for films, fibers, tapes, molding compositions, graphic or paint materials, in particular powder paints, adhesives or putty.

Polyolefins stabilized in this way can be used in various forms, in particular as thick layered polyolefins which are in prolonged contact in the extraction medium, for example in pipes, films, geomembrane, strips, profiles or tanks for liquids or gases.

Preferred thick layered polyolefin moldings have a thickness of 1 to 50 mm, in particular 1 to 30 mm, for example 2 to 10 mm.

As mentioned above, the organic material to be protected is preferably an organic, in particular a synthetic polymer. In this regard, thermosetting materials are particularly advantageous. In this connection, the emphasis is on the excellent action of the novel stabilizer mixtures of components (b), (c), (d) and (e) as process stabilizers (heat stabilizers). For this purpose, they are advantageously added to the polymer during or before processing. However, other polymers (such as elastomers) or lubricants or aqueous liquids can be stabilized against degradation, such as light-induced or thermal-oxidative degradation. Elastomers can be used from the organic materials listed above.

The lubricant or aqueous liquid is for example based on mineral oil or synthetic oil or mixtures thereof. Lubricants are known to those skilled in the art and are described in related technical literature, such as Dieter Klamann, "Schmierstoffe und verwandte Produkte" (Verlag Chemie, Weinheim, 1982), Schewe-Kobek, "Das Schmiermittel-Taschenbuch" (Dr. Alfred Huthig). Verlag, Heidelberg, 1974) and "Ullmanns Enzyklopadie der technischen Chemie", Vol. 13, pp. 85-94 (Verlag Chemie, Weinheim, 1977).

Preferred embodiments of the present invention therefore constitute components (b), (c) in particular as stabilizers for stabilizing organic materials, in particular thermosetting polymers against oxidation, heat or photo-induced decomposition, in particular as processing stabilizers (heat stabilizers). ), (d) and (e).

The invention also

(i) at least one benzofuran-2-one type compound,

(ii) at least one compound selected from the group of organic phosphites or phosphonites,

(iii) at least one compound selected from the group of phenolic antioxidants, and

(iv) a stabilizer mixture comprising at least one compound selected from the group of sterically hindered amines.

Preference is given to a weight ratio of components (i) :( ii) :( iii) :( iv) of 10: 1: 1: 0.1 to 0.01: 1: 10: 100, in particular 5: 1: 1: 0.1 to 0.01: 1: Stabilizer mixture of 1:10.

The novel stabilizer mixtures of components (b), (c), (d) and (e) have good stability against hydrolysis and advantageous color properties, ie, almost no discoloration of organic materials during processing.

Organic materials stabilized with the components of the present invention are particularly well protected against photo-induced decomposition.

The present invention therefore provides a method for stabilizing an organic material from oxidation, heat or photo-induced decomposition, comprising incorporating or applying one or more of each component (b), (c), (d) and (e) to said material It is about.

Preference is given to incorporating or applying one or more of each component (b), (c), (d) and (e) into the polyolefin for long periods of contact with the extraction medium, the layer thickness being from 1 to 50 mm, in particular from 1 to 30 mm, For example, a method of stabilizing polyolefins, such as thick layer polyolefin moldings, which are 2 to 10 mm.

Of particular importance is a method of long-term contact with the extraction medium by incorporating or applying one or more of each component (b), (c), (d) and (e) into the molding, and stabilizing a thick layer of polyolefin molding as a pipe or lipid membrane. to be.

The meaning of a lipid membrane is, for example, a film used in landfills and requiring a life of 300 years.

Extraction media are, for example, liquid or gas inorganic or organic materials.

Examples of gaseous inorganic materials include oxygen; nitrogen; Oxides of nitrogen; For example, NO, NO ₂ ; Oxides of sulfur such as sulfur dioxide; Halogen, such as fluorine or chlorine; Bronsted acid, such as hydrofluoric acid, hydrochloric acid, bromic acid, iodic acid or cyanic acid; Or a base such as ammonia.

Examples of gaseous organic materials include alkanes of C ₁ -C ₄ , such as methane, ethane, propane or butane; carbon monoxide; carbon dioxide; Or phosgene.

Examples of liquid inorganic materials include water, chlorinated drinking water or water soluble salt solutions, such as sodium chloride solution (saline) or sodium sulfate solution; bromine; Acid halides such as titanium tetrachloride, thionyl chloride, nitrosyl chloride or trimethylsilyl chloride; Alkali, such as aqueous sodium hydroxide (NaOH), aqueous potassium hydroxide (KOH), aqueous ammonia solution, aqueous sodium bicarbonate solution or aqueous sodium carbonate solution.

Examples of liquid organic materials are organic solvents or liquid organic reagents.

Examples of organic solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, petroleum fraction, nonane or decane; Alcohols such as methanol, ethanol, isopropanol, butanol, pentanol, amyl alcohol, cyclohexanol, pentaerythroitol, ethylene glycol, ethylene diglycol, methylcellulose solution, polyethylene glycol or glycerol; Ketones such as acetone, diethyl ketone, methyl ethyl ketone, diphenyl ketone or cyclohexanone; Ethers such as diethyl ether, dibutyl ether, tetrahydrofuran or dioxane; Aromatic hydrocarbons such as benzene, toluene or xylene; Heterocyclic solvents such as furan, pyridine, 2,6-lutidine or thiophene; Dipolar semiprotic solvents such as dimethylformamide, diethylacetamide or acetonitrile; Or surfactants.

For the purposes of the present invention, the extraction medium is a mixture and solution of the liquid or gas inorganic and organic substances described above, in particular an aqueous mixture, emulsion or solution.

Of particular importance are extraction media which are important in the chemical industry or in landfills.

Thus, a preferred embodiment of the present invention is a stabilizer mixture of components (b), (c), (d) and (e) together with other additives as necessary to improve the stability of the polyolefins in prolonged contact with the extraction medium. Is to use

Preferred components (b), (c), (d) and (e) for use as stabilizers, methods for stabilization and stabilizer mixtures are as described above in the composition together with organic materials.

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

Example 1 Stabilization of Polyethylene in Prolonged Contact with Water.

0.1% by weight of calcium stearate and the stabilizers described in Table (1) were added dry to a polyethylene polymer (Hostalen ^R CRP 100; PE-HD) taken directly from the reactor, and the additives were incorporated in a Pappenmaier mixer (type 20) for 2 minutes. (Examples 1a to 1c).

Example Stabilizer Volume (% by weight) Example 1a ^a) Irgafos ^R 168 ^c) Irganox ^R 1010 ^d) Chimassorb ^R 944 ^e) 0.100.100.20 Example 1b ^b) Verbindung (101) ^f) Irgafos ^R 168 ^c) Irganox ^R 1010 ^d) Chimassorb ^R 944 ^e) 0.050.100.050.20 Example 1c ^b) Verbindung (101) ^f) Irgafos ^R 168 ^c) Irganox ^R 1010 ^d) Chimassorb ^R 119 ^e) 0.050.100.050.20

a) Comparative Example.

b) embodiments according to the invention

c) Irgafos ^R 168 (Ciba Spezialitatenchemie AG) is tris (2,4-di-tert-butylphenyl) phosphite.

d) Irganox ^R 1010 (Ciba Spezialitatenchemie AG) is a pentaerythroitol ester (compound of formula (6c)) of 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid.

e) Chimassorb ^R 944 (Ciba Spezialitatenchemie AG) provides N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6 -Shows a linear or cyclic condensation product prepared from dichlor-1,3,5-triazine [compound of formula (28e)].

f) Compound 101 is a mixture of about 85 parts by weight of compound of formula 5a and about 15 parts by weight of compound of formula 5b.

g) Chimassorb ^R 119 (Ciba Spezialitatenchemie AG) is 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3, The condensation product prepared from 5-triazine and 1,2-bis (3-aminopropylamino) ethane is shown [compound of formula (28f)].

Irgafos ^R 168, Irganox ^R 1010, Chimassorb ^R 944 and Chimassorb ^R 119 are protected under the trade names of Ciba Spezialitatenchemie AG.

In the Schwabenthan extruder, the polyethylene to be stabilized was homogenized at 220 ° C. and granulated at 300 ° C. A test sheet measured 44 mm wide, 20 mm long and 2 mm thick for extrusion experiments in water was pressed from the granules of each formulation (Examples 1a-1c) using a bench press. To facilitate demoulding of the test sheet, compression was performed between two aluminum foils.

Stabilizer extraction experiments were conducted in deionized water. Heat control of the extraction vessel was carried out in a Heraeus (Hanau, Germany) convection oven with a maximum temperature deviation of 1.5 ° C. In order to conduct extraction experiments below the boiling point of water, glass containers were used. A stainless steel pressure vessel was used when the water temperature was 105 ° C. Because of the risk of water being supersaturated with stabilizers, the amount of liquid used in the experiments was fixed at 400 ml per approximately 70 g of polymer, and water was replenished with clean water at regular intervals, especially after sampling.

The test sheet was subjected to the conditions described above at 80 ° C. for 50 days. After the extraction experiment was finished, the amount of residual stabilizer and oxidation induction time (OIT) of the test sheet was measured.

The residual amount of sterically hindered phenol, Irganox ^R 1010, was measured by UV / VIS detectors of Spectra Physics SP 8800 and Spectra 200 with automatic sampler. Chromatography was performed on a hyperchrome 125 × 4.6 mm column filled with Nucleosil C 185 μm at room temperature. The injected volume was 14 μl at a flow rate of 1.5 ml / min. UV measurement was performed at 270 nm.

The residual amounts of triazine containing sterically hindered amines, Chimassorb ^R 944 and Chimassorb ^R 119 were determined by measuring the difference in absorption at 246.4 and 300 nm with a Perkin Elmer Lambda 15 type UV spectrometer.

Oxidation induction time was measured from the TA instrument (Alzenau, Germany) by a "DuPont instrument 910, differential scanning calorimeter" and with a sample volume of 5-10 mg, with constant thermal stress (190 ° C) until the complete decomposition of the polyethylene sample began. Under C / O ₂ ), the period of time is described in minutes. The longer the oxidation induction time, the more stable the polystyrene and the more stable the polyethylene with respect to the extracted water in contact with the polyethylene for a long time.

The results show that if the stabilizer mixture comprises novel components (b), (c), (d) and (e), the stability of the polyolefin in contact with the extraction medium for an extended period of time is improved.

The results are shown in Table (2).

Water shelf life for 50 days at 80 ℃ Example Stabilizer Residual stabilizer content after 50 days at 80 ° C Oxidation Induction Time (min) Example 1a ^a) 0.10% Irgafos ^R 168 ^c) 0.10% Irganox ^R 1010 ^d) 0.20% Chimassorb ^R 944 ^e) 52% 57% 34 Example 1b ^b) Verbindung (101) ^f) 0.10% Irgafos ^R 168 ^c) 0.05% Irganox ^R 1010 ^d) 0.20% Chimassorb ^R 944 ^e) 56% 71% 38 Example 1c ^b) 0.05% Verbindung (101) ^f) 0.10% Irgafos ^R 168 ^c) 0.05% Irganox ^R 1010 ^d) 0.20% Chimassorb ^R 119 ^e) 57% 70% 39

See footnotes a) to g) for table (1).

Example 2 Multiple Compression and Stabilization of Polypropylene, Especially at High Temperatures.

1.5 kg of polypropylene powder (Profax ^R 6501) initially stabilized with 0.008% Irganox ^R 1076 (compound of formula (6b)) (melt index 3.2 measured at 230 ° C. and 2.16 kg) was added 0.10% calcium stearate and It was mixed with 0.015 to 0.20% of the stabilizers listed in Table (3). The mixture was extruded at 100 rpm in an extruder with a diameter of 20 mm and a length of 400 mm, with a maximum extrusion temperature of 280, 300, 320 and 340 ° C. To cool, the extrudate was passed through a water bath and then granulated. These granules were repeatedly extruded. After five extrusions, the melt index was measured (at 230 ° C. and 2.16 kg). Higher melt indexes indicate severe chain breaks, which means lower stability. The results are shown in Table (3). This indicates that the stability of the polypropylene is improved if the stabilizer mixture comprises novel components (b), (c), (d) and (e).

Water shelf life for 50 days at 80 ℃ Example Stabilizer Volume (% by weight) Melt Index After Five Extrusions Example 2a ^a) Irgafos ^R 168 ^c) Irganox ^R 1010 ^d) Chimassorb ^R 944 ^e) 0.100.100.20 17.5 Example 2b ^b) Verbindung (101) ^f) Irgafos ^R 168 ^c) Irganox ^R 1010 ^d) Chimassorb ^R 944 ^e) 0.0150.100.050.10 8.6 Example 2c ^b) Verbindung (101) ^f) Irgafos ^R 168 ^c) Irganox ^R 1010 ^d) Chimassorb ^R 119 ^e) 0.0150.100.050.10 8.0

See footnotes a) to g) for table (1).

As stabilizers, organic materials comprising at least one benzofuran-2-one type compound, at least one organic phosphite or phosphonite type compound, at least one phenolic antioxidant type compound and at least one sterically hindered amine type compound are oxidized, Or excellent stability to photo-induced decomposition.

Claims (9)

a) organic matter susceptible to oxidation, heat or light-induced degradation; b) at least one benzofuran-2-one type compound, c) at least one compound selected from the group of organic phosphites or phosphonites, d) at least one compound selected from the group of phenolic antioxidants and e) a composition comprising at least one compound selected from the group of sterically hindered amines. The composition of claim 1 comprising as component (b) a compound of formula (1): (One) Where n is 1, R ₁ is unsubstituted or C ₁ -C ₄ alkyl-, C ₁ -C ₄ alkoxy-, C ₁ -C ₄ alkylthio-, hydroxy-, halo-, amino-, C ₁ -C ₄ alkylamino-, Phenylamino- or di (C ₁ -C ₄ alkyl) amino-substituted naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetra Hydro-1-naphthyl, thienyl, benzo [b] thienyl, naphtho [2,3-b] thienyl, thianthrenyl, dibenzofuryl, chromenyl, xanthenyl, phenoxatiinyl, pi Rollyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolinyl, isoindolyl, indolyl, indazolyl, furinyl, quinolzynyl, isoquinolyl, quinolyl, phthala Genyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnaolinyl, putridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl , Isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, pool A carbonyl or fluorescein page noksa or possess, or R ₁ is for a radical of formula (2), (2) And if n is 2, R ₁ is unsubstituted or C ₁ -C ₄ alkyl- or hydroxy-substituted phenylene or naphthylene; Or -R ₁₂ -XR _13- , R ₂ , R ₃ , R ₄ and R ₅ are independently of each other hydrogen, chlorine, hydroxy, C ₁ -C ₂₅ alkyl, C ₇ -C ₉ phenylalkyl, unsubstituted or C ₁ -C ₄ alkyl-substituted phenyl; Unsubstituted or C ₁ -C ₄ alkyl-substituted C ₅ -C ₈ cycloalkyl; C ₁ -C ₁₈ alkoxy, C ₁ -C ₁₈ alkylthio, C ₁ -C ₄ alkylamino, di (C ₁ -C ₄ alkyl) amino, C ₁ -C ₂₅ alkanoyloxy, C ₁ -C ₂₅ alkanoyl Amino, C ₃ -C ₂₅ alkenoyloxy, oxygen in the middle of the chain, sulfur or C ₃ -C ₂₅ alkanoyloxy comprising; C ₆ -C ₉ cycloalkylcarbonyloxy, benzoyloxy or C ₁ -C ₁₂ alkyl-substituted benzoyloxy; Or other radicals R ₂ and R ₃ or the radicals R ₃ and R ₄ or the radicals R ₄ and R ₅ together with the carbon atoms attached thereto form a benzo ring, wherein R ₄ is additionally-(CH ₂ ) _{if p} -COR ₁₅ or-(CH ₂ ) _q OH or if R ₃ , R ₅ and R ₆ are hydrogen, R ₄ is additionally a radical of formula (3), (3) R ₁ is defined as described above when n = 1, R ₆ is hydrogen or a radical of formula (4), (4) R ₄ is not a radical of formula (3) and R ₁ is defined as described above when n = 1, R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ are independently of each other hydrogen, halogen, hydroxy, C ₁ -C ₂₅ alkyl, oxygen, sulfur or C ₂ -C ₂₅ alkyl comprising; C ₁ -C ₂₅ alkoxy, oxygen, sulfur or C ₂ -C ₂₅ alkoxy comprising; C ₁ -C ₂₅ alkylthio, C ₃ -C ₂₅ alkenyl, C ₃ -C ₂₅ alkenyloxy, C ₃ -C ₂₅ alkynyl, C ₃ -C ₂₅ alkynyloxy, C ₇ -C ₉ phenylalkyl, C ₇ -C ₉ phenylalkoxy, unsubstituted or C ₁ -C ₄ alkyl-substituted phenyl; Unsubstituted or C ₁ -C ₄ alkyl-substituted phenoxy; Unsubstituted or C ₁ -C ₄ alkyl-substituted C ₅ -C ₈ cycloalkyl; Unsubstituted or C ₁ -C ₄ alkyl-substituted C ₅ -C ₈ cycloalkoxy; C ₁ -C ₄ alkylamino, di (C ₁ -C ₄ alkyl) amino, C ₁ -C ₂₅ alkanoyl, oxygen, sulfur or C ₃ -C ₂₅ alkanoyl comprising; C ₁ -C ₂₅ alkanoyloxy, oxygen, sulfur or C ₃ -C ₂₅ alkanoyloxy comprising; C ₁ -C ₂₅ alkanoylamino, C ₃ -C ₂₅ alkenoyl, oxygen, sulfur or C ₃ -C ₂₅ alkenoyl comprising; C ₃ -C ₂₅ alkenoyloxy, oxygen, sulfur or C ₃ -C ₂₅ alkenoyloxy comprising; C ₆ -C ₉ cycloalkylcarbonyl, C ₆ -C ₉ cycloalkylcarbonyloxy, benzoyl or C ₁ -C ₁₂ alkyl-substituted benzoyl; Benzoyloxy or C ₁ -C ₁₂ alkyl-substituted benzoyloxy; or Or else, in formula (2), the radicals R ₇ and R ₈ or the radicals R ₈ and R ₁₁ join together with the carbon atoms attached to them to form a benzo ring, R ₁₂ and R ₁₃ are independently of each other unsubstituted or C ₁ -C ₄ alkyl-substituted phenylene or naphthylene, R ₁₄ is hydrogen or C ₁ -C ₈ alkyl, R ₁₅ is hydroxy, , C ₁ -C ₁₈ alkoxy or ego, R ₁₆ and R ₁₇ are independently of each other hydrogen, CF ₃ , C ₁ -C ₁₂ alkyl or phenyl, or R ₁₆ and R ₁₇ are unsubstituted or C ₁ -C ₄ alkyl together with the C atom attached thereto; To form one to three substituted C ₅ -C ₈ cycloalkylidene rings; R ₁₈ and R ₁₉ are independently of each other hydrogen, C ₁ -C ₄ alkyl or phenyl, R ₂₀ is hydrogen or C ₁ -C ₄ alkyl, R ₂₁ is hydrogen, unsubstituted or C ₁ -C ₄ alkyl-substituted phenyl; C ₁ -C ₂₅ alkyl, oxygen, sulfur or C ₂ -C ₂₅ alkyl comprising; C ₇ -C ₉ phenylalkyl substituted one to three times by C ₁ -C ₄ alkyl on an unsubstituted or phenyl radical; Substituted 1-3 times with C ₁ -C ₄ alkyl on an unsubstituted or phenyl radical, with oxygen, sulfur or C ₇ -C ₂₅ phenylalkyl, or, or any other radical R ₂₀ and R ₂₁ are unsubstituted with one carbon atom attached to these, or C ₁ -C ₄ alkyl, one to three times substituted by a C ₅ -C, including Forms a ₁₂ cycloalkylene ring; R ₂₂ is hydrogen or C ₁ -C ₄ alkyl, R ₂₃ is hydrogen, C ₁ -C ₂₅ alkanoyl, C ₃ -C ₂₅ alkenoyl, oxygen, sulfur or C ₃ -C ₂₅ alkanoyl comprising; C ₂ -C ₂₅ alkanoyl substituted by di (C ₁ -C ₆ alkyl) phosphonate groups; C ₆ -C ₉ cycloalkylcarbonyl, tenoyl, furoyl, benzoyl or C ₁ -C ₁₂ alkyl-substituted benzoyl; or ego, R ₂₄ and R ₂₅ are independently of each other hydrogen or C ₁ -C ₁₈ alkyl, R ₂₆ is hydrogen or C ₁ -C ₈ alkyl, R ₂₇ is a direct bond, C ₁ -C ₁₈ alkylene, oxygen, sulfur or C ₂ -C ₁₈ alkylene comprising a; C ₂ -C ₁₈ alkenylene, C ₂ -C ₂₀ alkylidene, C ₇ -C ₂₀ phenylalkylidene, C ₅ -C ₈ cycloalkylene, C ₇ -C ₈ bicycloalkylene, unsubstituted or C _1- C ₄ alkyl-substituted phenylenes, or ego, R ₂₈ is hydroxy, , C ₁ -C ₁₈ alkoxy or ego, R ₂₉ is oxygen, -NH- or ego, R ₃₀ is C ₁ -C ₁₈ alkyl or phenyl, R ₃₁ is hydrogen or C ₁ -C ₁₈ alkyl, M is a r-valent metal cation, X is a direct bond, oxygen, sulfur or -NR _31- , n is 1 or 2, p is 0, 1 or 2, q is 1, 2, 3, 4, 5 or 6, r is 1, 2 or 3, and s is 0, 1 or 2. The composition of claim 1 comprising as component (c) a compound of formula (14), (15), (18) or (19): (14) (15) (18) (19) In the above formula, n 'is 2 and y' is 1, 2 or 3; A 'is C ₂ -C ₁₈ alkylene, p-phenylene or p-biphenylene, E ′ is C ₁ -C ₁₈ alkyl, —OR ′ ₁ or fluorine when y ′ is 1; E 'is p-biphenylene when y' is 2, E 'is N (CH ₂ CH ₂ O-) ₃ when y' is 3; R ' ₁ , R' ₂ and R ' ₃ are independently of each other C ₁ -C ₁₈ alkyl, C ₇ -C ₉ phenylalkyl, cyclohexyl, phenyl or 1 to 3 alkyl radicals having a total of 1 to 18 carbon atoms Phenyl substituted by; R _'14 is hydrogen or C ₁ -C ₉ alkyl, R _'15 is hydrogen or methyl, X ’is a direct bond, Y 'is oxygen, Z 'is a direct bond or -CH (R' ₁₆ )-, and R _'16 is C ₁ -C ₄ alkyl. The composition of claim 1 comprising as component (d) a compound of formula (6): (6) In the above formula, R ₁ is C ₁ -C ₄ alkyl, n is 1, 2, 3 or 4, X is methylene, or ego, Y is oxygen or -NH-; If n is 1, X is Where Y is attached to R ₂ , R ₂ is C ₁ -C ₂₅ alkyl; if n is 2, X is Where Y is attached to R ₂ , R ₂ is C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkylene comprising oxygen or sulfur in the middle of the chain; Or if Y is -NH-, R ₂ is additionally a direct bond; if n is 3, X is methylene or Wherein the ethylene group is attached to R ₂ , R ₂ is ego; And if n is 4, X is Where Y is attached to R ₂ , R ₂ is C ₄ -C ₁₀ alcantetrayl. The composition of claim 1 wherein component (e) comprises at least one radical of formula (12) or (13): (12) (13) In the above formula, G is hydrogen or methyl, and G ₁ and G ₂ are hydrogen, methyl or oxygen together. The composition of claim 1 comprising as component (a) a natural, semisynthetic or synthetic polymer. The composition of claim 1 further comprising other additives in addition to components (a), (b), (c), (d) and (e). (i) at least one benzofuran-2-one type compound, (ii) at least one compound selected from the group of organic phosphites or phosphonites, (iii) at least one compound selected from the group of phenolic antioxidants, and (iv) at least one compound selected from the group of sterically hindered amines, wherein the weight ratio of components (i) :( ii) :( iii) :( iv) is from 10: 1: 1: 0.1 to 0.01: 1: 10 Stabilizer mixture which is: 100. Stabilizing the organic material from oxidation, heat or photo-induced decomposition, comprising incorporating or applying one or more of each component (b), (c), (d) and (e) according to claim 1 to the organic material. How to let.