EP1192213A1 - Stabilization of plastics and articles produced or coated therewith - Google Patents

Abstract

The present invention relates to the use of compounds of formula (I) whose substituents are as defined in claim 1 for the stabilization of reinforced thermoplastics, plastic substrates or plastic-coated substrates during their preparation and processing, and of plastics during injection molding by the hot runner technique.

Description

STABILIZATION OF PLASTICS AND ARTICLES PRODUCED OR COATED THEREWITH.

The present invention relates to the use of compounds of the formula (I)

in which

R^a, R°, R^d, R^e, R^f, R⁹ and R^h independently of one another are hydrogen, hydroxyl, d-C^alkyi, unsubstituted or mono-, di- or tri-Cι-C₄alkyl-substituted phenyl, C₇-C₉phenylalkyl, unsubstituted or mono-, di- or tri-Cι-C₄alkyl-substituted C₅-Cι₂cycloalkyl or C Ciβalkoxy and R^c is as defined above for R^a, R^b, R^d, R^e, R^f, R⁹ and R^h or is a radical of the formula (II)

in which

R^a, R°, R^d, R^e, R^f, R⁹ and R^h are as defined above and R' and R¹ independently of one another are hydrogen or C -C₄alkyl, at least two of the radicals R^d, R^e, R^f, R⁹ and R^h being hydrogen, for the stabilization of reinforced thermoplastics, plastic substrates or plastic-coated substrates during their preparation and processing, and of plastics during injection molding by the hot runner technique.

Preference is given to the use in accordance with the invention of compounds of the formula I in which

R^b is hydrogen and/or

R^d-R^h are hydrogen and/or

R^a and R^c are CrC₁₈alkyl, especially tert-butyl, or unsubstituted or mono-, di- or tri- Crdalkyl-substituted phenyl.

If R^c is a radical of the above formula II then R' and R' are preferably both methyl.

Reinforced thermoplastics have been widely developed for specific applications in which excellent mechanical stability is in the foreground; cf. H. Saechtling, "Kunststoff- Taschenbuch", 26^th Edition (1995); Carl Hanser Verlag, Munich - Vienna; sections 3.2.1.5, p. 203 and 5.3.2, p.595.

The reinforcing component can comprise glass beads, talc, mica, glass fibers, carbon fibers, polymer fibers such as poly-p-phenyleneterephthalamide (Kevlar®), for example, or continuous fibers of thermoplastic liquid-crystalline polymers, and also natural fibers and a large number of organic or inorganic nanomaterials.

Conventional precursors (known as prepregs) are produced by melting, impregnating or laminating the reinforcing filler phase (woven fabric, fibers, etc.) with a thermoplastic polymer to give a semi-finished product. After heating, with or without the action of external pressure, the composite is made suitable for further processing on the basis of relatively large plasticity or relatively low viscosity of the polymeric matrix. Various technical processes are based on pultrusion, in which parts preheated in this way are used to produce end products; cf. W. Michaeli and J. Blaurock, Kunststoffe, 88, 5, pp. 685-688 (1998).

Optimum impregnation requires that the polymer matrix is able to penetrate the reinforcing filler phase without hindrance. The extent of penetration is a critical parameter for the production of reinforced thermoplastics. One precondition is adequate adhesive strength between the reinforcing filler phase and the polymer matrix. At relatively high processing temperatures, a relatively low viscosity of the thermoplastic polymer often allows these essential requirements to be met. However, it has been found to be disadvantageous that the use of relatively high temperatures is often accompanied by partial decomposition of the matrix polymer.

Applications for a functional coating embrace a large range of products. Individually, the products are subdivided according to the type of substrate, the type of polymer coating used, the adhesive strength between substrate and polymer phase and, finally, possible further layers which may build up a multilayer system. The substrate can comprise paper, board, metals and plastics with a well-defined surface, or else fibers (based on textile nonwovens, for example). The plastics phase used as the coating generally comprises polyolefins or polyolefin copolymers. In terms of volume, LD polyethylene continues to dominate many applications (e.g. paper coating).

The adhesive strength between the substrate and the coated plastics phase increases constantly with the temperature during the coating operation and/or during the subsequent curing phase. Apart from the fact that coupling agents are often used to improve the interphase adhesion, the temperature is an unavoidable parameter for obtaining the required stability of the end product.

Processing procedures involving extrusion are in many cases linked to specific geometries of the processing machine. In the case of injection molding technology in particular, the region from the space in front of the screw to the gate of the mold, known as the hot runner, is of critical importance for appropriate thermal control of the polymer melt. The ideal temperature of this region is precisely the melt temperature, which is also generated by heating the screw casing and/or, if appropriate, the screw itself. The consequence of this is that there should be no heat exchange between the polymer melt and the hot runner system (including the hot runner and machine nozzle). In fact, however, temperature regulation depends on the nature and quality of the temperature regulators used and on the configuration of the hot runner, including its locally adjusted temperature sensor. An optimum arrangement frequently fails on mechanical grounds even at the construction stage. Often, the local temperature measurement fails to detect significant cyclic and stationary temperature differences in the hot runner zone. This gives rise to processing problems owing to altered viscosity of part of the polymer melt, polymer degradation due to local overheating, and deformation in the subsequent part of the material. In conventional hot runner systems, improved energy distribution can be ensured only at great technical expense; for instance, by installing heat conductor pipes. Even the use of conventional stabilizer systems is unable to afford the respective polymer adequate protection against degradation in the hot runner, and in practice often leads to unwanted effects such as embrittlement and discoloration, for example. The processing of plastics by the various known methods requires at least one heat treatment. In order to avoid decomposition by oxidation, chain scission or other decomposition processes the presence of suitable stabilizers or stabilizer combinations is vital. Conventional stabilizer systems comprise mixtures of organophosphites or organophosphonites, sterically hindered amines and/or phenols. In the majority of cases , as well, costabilizers based on metal salts (e.g. calcium stearate) are added in order to modify the activity of the stabilizers.

It is possible, furthermore, to add co-additives such as metal deactivators, plasticizers, UV absorbers, hydroxylamines, nitrones, color improvers, optical brighteners, thiosynergists, peroxide scavengers, buffer systems, nucleating agents, pigments, dyes, flame retardants, antistats and emulsifiers in concentrations of between 0.0001 % and 30%. The system in question may also include conventional fillers in a concentration range from 0.01% to 70%.

For a number of years it has been known that certain industrially important high-temperature processes such as, for example, the production process of polyolefin fibers, the rotomolding process, pipe extrusion or the production of cable sheathing can be practiced more advantageously by adding small concentrations of 3-phenylbenzofuranones; cf. DE-A-197 28 214, EP-A-842975 and EP-A-839623. It is assumed that, during the processing step, conversion products of the 3-phenylbenzylfuranones react rapidly with thermally generated radicals of the polymers in the melt.

The compounds of the benzofuran-2(3H)one class have already been known for a long time.

The use of these compounds as stabilizers for organic material was described, inter alia, in WO 80/01566 (priority 02.05.1979) and in DE 2354995. WO 80/01566 describes not only 3-arylbenzofuranones carrying the unsubstituted phenyl radical in position 3 (Table 1 in WO 80/01566) but also 3-arylbenzofuranones which carry variously substituted aromatic systems in position 3 (Table 2 in WO 80/01566) and its compounds 58-60 as stabilizers.

Even at low concentrations, 3-phenylbenzofuranones, when used in combination with conventional stabilizers such as organophosphites and organophosphonites, sterically hindered amines and/or, optionally, phenolic antioxidants, ensure excellent stability of the polymer melt. Totally unexpectedly, a specific subgroup of the benzofuranones described in WO 80/01566, namely the compounds of the formula I defined at the outset, has been found to possess an especially outstanding suitability in the stabilization of reinforced thermoplastics during their preparation and processing and in the stabilization of plastics or plastic-coated substrates during their production and processing, and in the stabilization of plastics during injection molding by the hot runner technique. Where, in a 3-phenylbenzofuran-2-one, the phenyl radical in position 3 has at least two hydrogen atoms and there is a hydrogen atom on the benzofuranone system in position 4, an amazingly high level of activity is found in the abovementioned use in accordance with the invention.

The compounds of the formula I can, in accordance with the invention, also be used advantageously in combination with other stabilizers, especially in combination with organophosphites and/or organophosphonites plus, if desired, sterically hindered phenols and/or sterically hindered amines (HALS). The combinations may further comprise acid scavengers (basic costabilizers) as well; in combinations containing sterically hindered phenols, costabilizers containing sulfur may also be present advantageously.

The compounds of the formula I are used judiciously in a concentration range of 0.001-5%, preferably 0.002-0.05%; each of the other components can be present in a concentration range of 0.001-5%, preferably 0.01-1.0%.

Suitable sterically hindered amines for the purposes of the present invention include both monomeric and polymeric HALS stabilizers, and also combinations of polymeric with monomeric HALS stabilizers, as described, for example, in EP-A-80431 and EP-A-632092.

The use of 3-phenylbenzofuranones of the formula I according to the invention, especially in combination with organophosphites or organophosphonites, sterically hindered amines and/or sterically hindered phenols, results in advantageous, efficient stabilization of thermoplastic polymers containing integrated reinforcing fillers. The advantageous activity of the 3-phenylbenzofuranones of the formula I is manifested particularly during the preparation of such reinforced materials, even and specifically when high processing temperatures are employed. To a considerable extent, the 3-phenylbenzofuranones of the formula I suppress typical decomposition and degradation processes, such as chain scission, in the polymer matrix, thereby suppressing embrittlement and discoloration processes and so extending the useful life of the material in question. The possibility of using high processing temperatures in the presence of 3-phenylbenzofuranones of the formula I permits, moreover, the development of relatively strong adhesion forces in the phase between the reinforcing filler and its surrounding polymer matrix and in the phase between the solid substrate and the respective polymer layer.

The present invention, then, permits the use of more efficient stabilizer systems comprising 3-phenylbenzofuranones of the formula I for production processes involving the production of reinforced thermoplastic polymers by lamination, extrusion, pultrusion or other processes. The use of the 3-phenylbenzofuranones of the formula I not only allows reinforced thermoplastic polymers to be prepared with reduced decomposition but also brings about improved anchoring of the reinforcing filler phase in the polymer matrix.

The reinforcing fillers (such as glass beads, talc, mica, glass fibers, carbon fibers, polymer fibers such as poly-p-phenyleneterephthaiamide (Kevlar®) or continuous fibers of thermoplastic liquid-crystalline polymers and of natural fibers, and a large number of organic or inorganic nanomatehals (see above) can be used in concentrations of between 0. 0001% and 30%. The system in question may also contain conventional fillers in a concentration range from 0.01% to 70%.

Typical representatives of thermoplastic polymers include polypropylene (PP) and PP copolymers, polyethylene (PE-HD, PE-LD, PE-MD, PE-LLD), polyamide, polyesters, polyphenylene sulfide, polyether ketone, polycarbonate, polyetherimide, styrene-acrylonitrile polymers, polyether sulfone, polyaryl ether sulfone, polyamideimide, polyethylene terephthalate, polybutylene terephthalate, polysulfone, and their respective blend systems.

Further representatives include polymer laminates produced by means of high-frequency corona effects at high temperatures. This technology can be used to obtain materials with a strong interaction between matrix polymer and reinforcing fiber.

Other applications relate to the lamination and/or impregnation of fibers attached to polymer substrates (used, for example, for structural components in the automotive interior sector).

Suitable quite generally are materials consisting of thermoplastics and reinforcing fillers which are present in the concentration range between 0.1 % and 50% in the matrix of thermoplastic polymers. The use of stabilizer systems based on specific 3-phenylbenzofuranones makes it possible to conduct coating processes on appropriate substrates even at a relatively high temperature. The use of 3-phenylbenzofuranones of the formula I not only makes it possible to produce coating systems with relatively little decomposition but also results in improved adhesion of the polymer layer to the respective substrate. Furthermore, conditions are created in which such products can be produced at greater throughput.

Any coating method is suitable for the invention, especially the extensive field of extrusion coating and of high-speed extrusion coating, but also the production of multilayer systems.

Other processes suitable for the invention are those permitting double-sided coating of the substrate with the polymer layer, in order, for instance, to be able to produce two- dimensional arrangements better. Furthermore, the polymer can also be applied in the form of polymer/wax dispersions, in order finally to form continuous films on the substrate.

Further processes in accordance with the invention are the following:

The process known as immersion, where the substrate is immersed in the solution or dispersion of the polymer. Following its slow removal, there is generally a thin polymer layer left on the substrate, whose adhesion is improved by evaporating the solvent(s) and, if desired, by curing at high temperatures.

The process known as powder coating, where the respective polymer powder is distributed into the voids of a porous substrate plate using an overpressure that generates a fluidized bed. When the plate, preheated to 200-400°C, is immersed in the polymer powder, an impermeable polymer layer is formed within a few seconds and can additionally be cured in a further step. Typically, the layer thicknesses of the polymer phase are in the range between 75 μm and 500 μm.

The process known as electrostatic coating, in the course of which the polymer powder present in a gun of appropriate construction is introduced into a high-voltage field (typically 50-90 kV) and charged such that it deposits on an earthed substrate. Subsequently, the polymer powder is melted in an oven, forming a generally smooth polymer layer (typical layer thickness 50 μm - 300 μm) on the substrate; cf. H. Saechtiing, "Kunststoff-Taschenbuch", 26^th Edition (1995); Carl Hanser Verlag, Munich, Vienna; section 3.2.9.3, p. 255. The process known as flame spraying, where the polymer powder is passed through the hot gas of a flame spraying gun and melted on a preheated substrate.

Other applications relate to the coating of fibers or nonwovens on polymer substrates in order to achieve improved impregnation.

The use of the compounds of the formula I in accordance with the invention enables injection molded articles produced using the hot runner technique to be manufactured reproducibly in good quality, in a modification and expansion of conventional stabilizing concepts. Possible dwell times, which are caused, for example, by operational conditions and which often lead to temporary and local overheating of the polymer melt, can be bridged without harm by rendering thermally generated carbon radicals in the polymer melt harmless, by means of rapid and efficient reaction with the radicals of 3-phenylbenzofuran-2-one of the formula I or of its successor products, these radicals being formed in situ.

Through the use of processing stabilizers based on 3-phenylbenzofuran-2-ones it is possible greatly to suppress or even totally to avoid the abovementioned disadvantages in the end product by means of efficient stabilization of the polymer melt, and to do so especially when using high processing temperatures. The present invention therefore permits more reliably the production of injection moldings which meet the specification.

Particularly advantageous monomeric HALS stabilizers are compounds of the formulae A1 to A10.

in which

R¹ is hydrogen, C₅-C₇cycloalkyl or a d-C^alkyl group and

R⁴ is either hydrogen or a Cι-C₂₂alkyl group, an oxygen radical O*, -OH, -NO, CH₂CN, benzyl, allyl, a d-C₃oalkoxy group, a C₅-C₁₂cycloalkyloxy group, a C₆-Cι₀aryloxy group, where the aryl radical can also be substituted further, a C₇-C₂₀aralkyloxy group, where the aryl radical can also be substituted further, a C₃-C₁₀alkenyl group, a C₃-C₆alkynyl group, a d-C₁₀acyl group, halogen, or C₇-C₉phenylalkyl which is unsubstituted or substituted on the phenyl ring by C₁-C₄alkyl, R⁶ is an aromatic radical substituted one or more times by hydrogen, Cι-C alkyl, d-C₄alkoxy, halogen, cyano, carboxyl, nitro, amino, d-C₄alkylamino, d-C₄diaikylamino or acyl, and o is 1 or 2;

in which

R and R⁴ are as defined above, p is 1 or 2 and

if p = 1

R⁷ is d-C₂₂alkyl, C₂-C₁₈oxaalkyl, C₂-C₁₈thiaalkyl, C₂-C₁₈azaalkyl or C₂-C₈alkenyl, and

if p = 2

R⁷ is d-d^alkylene, C -C ₈oxaalkylene, C₂-Cι₈thiaalkylene, C₂-Cι₈azaalkylene or C₂-C₈alkenylene;

in which

R¹ and R⁴ are as defined above,

R⁸ and R⁹ independently of one another are hydrogen, d-C₆alkyl, C₇-Cι₂aralkyl, C₇-C₁₂aryl or carboxylate, or R⁸ and R⁹ together are a tetra- or pentamethyl group;

A 4 A 5

in which

R and R⁴ are as defined above,

R² and R³ independently of one another are a hydrogen atom, a d-C₁₈alkyl group or, together with the carbon atom connecting them, are a ring with a ring size of from 5 to 13 or, together with the carbon atom connecting them, are a group of the formula (IV)

1 _R ¹

1 (IV)

R R

R⁴ and R⁵ independently of one another are either hydrogen or a C C₂₂alkyl group, an oxygen radical O*, -OH, -NO, CH₂CN, benzyl, allyl, a d-C₃oalkoxy group, a C₅-Cι₂cycloalkyloxy group, a C₆-C₁₀aryloxy group, where the aryl radical can also be substituted further, a C₇-C₂oarylalkyloxy group, where the aryl radical can also be substituted further, a C₃-C₁₀alkenyl group, a C₃-C₆alkynyl group, a d-C₁₀acyl group, halogen, or C₇-C₉phenylalkyl which is unsubstituted or substituted on the phenyl ring by d-C₄alkyl, q is 1 or 2,

_R10 is hydrogen, methyl, phenyl or carb-C₁-C₂ιalkoxy,

R¹¹ is hydrogen or methyl, R¹² if q = 1 is hydrogen, d-d_ϋalkyl, C -C₂₂alkenyl, C₅-C₁₂cycloalkyl or a radical of the formula

where

R¹ and R⁵ are as defined above, and

R¹² if q = 2 is d-C₁₈alkylene, C₅-C₉cycloalkylene or arylene;

where

R¹, R⁴, R⁷ and p are as defined above;

where

R¹, R⁴, R⁷ and p are as defined above;

where

R¹ and R⁴ are as defined above,

R³⁰ is hydrogen, d-d₂alkyl, C₅-C₁₂cycloalkyl, phenyl or C₇-C₉phenylalkyl, and a is a number from 1 to 10;

where

R¹ and R⁴ are as defined above and

R⁷ is as defined for p=1 in the formula A2;

a product A10 obtainable by reacting a polyamine of the formula A10a with formula A10b:

HRN (CH₂)_n NH (CH₂)_n NH (CH,) NHR'

5' 5" 5-»

R and R' = H , CH₃

(A10a)

where

R¹, R⁴ and R³⁰ are as defined above, and n₅', n₅- and n₅- independently of one another are a number from 2 to 12.

Preference is given to compounds of the formulae A1 to A10 in which

R¹ is hydrogen or a C₁-C alkyl group,

R² and R³ independently of one another are a hydrogen atom, a d-C₈alkyl group or, together with the carbon atom connecting them, are a ring with a ring size of from 6 to 12, or together with the carbon atom connecting them are a group of the formula (IV),

R⁴ and R⁵ independently of one another are either hydrogen or a d-C₅alkyl group, an oxygen radical O^*, -OH, -NO, -CH₂CN, benzyl, allyl, a C Cι₀alkyloxy group, a C₅-C₆cycloalkyloxy group, a C₆-C₇aryloxy group, where the aryl radical can also be substituted further; a C₇-C₁₀arylalkyloxy group, where the aryl radical can also be substituted further, a C₃-C₆alkenyl group, a C₃-C₆alkynyl group, a d-C acyl group, halogen, or C₇-C₉phenylalkyl which is unsubstituted or substituted on the phenyl ring by d-C₂alkyl,

R⁷ is a straight-chain d-C₁₀alkylene (if p = 2); or d-d₂alkyl (if p = 1 ),

R⁸ and R⁹ independently of one another are hydrogen, C₁-C₂alkyl, C₇-C₈arylalkyl, aryl or carboxylate, j 10 is hydrogen, methyl, phenyl or d-C₂alkoxy,

R¹ is hydrogen or methyl,

>12 if q = 1 is hydrogen, d-C₁₆alkyl, C₂-C₁₆alkenyl, C₅-C₆cycloalkyl or a radical of the formula

R¹² if q = 2 is d-d₆alkylene, C₅-C₆cycloalkylene or arylene,

R³⁰ is hydrogen, Cι-C₈alkyl, C₅-C₇cycloalkyl, phenyl or C₇-C₈phenylalkyl, a is from 1 to 5, o is 1 , and p is from 2 to 5.

Very particular preference is given to compounds of the formulae A1 to A10 in which

R¹ is methyl,

R² and R³ together with the carbon atom connecting them are a ring with a ring size of 12, or together with the carbon atom connecting them are a group of the formula (IV), R⁴ and R⁵ independently of one another are hydrogen, methyl, acetyl, octyloxy or cyclohexyloxy, R⁶ is p-methoxyphenyl,

R⁷ is octamethylene, hexamethylene or ethylene (if p = 2), or dodecyl (if p =1 ),

R⁸ and R⁹ are hydrogen, R¹⁰ is hydrogen,

R¹¹ is hydrogen,

R¹² is dodecamethylene or tetradecamethylene,

R³⁰ is cyclohexyl or n-butyl, a is 2, o is 1 , p is 2, and q is 1.

The following compounds are especially suitable in a mixture with compounds of the formula (I):

A'1

A' 2

A' 3

A' 6

A'7

A'8

A'9

A'10

A'11 A'12 A'13

RR'N-(CH2)₃-N-(CH₂)₂-N-(CH₂)₃-NRR' A'14

where R

and R' = H, CH₃

In one particularly suitable embodiment of the invention the stabilizers based on sterically hindered amines that are used are ^®Tinuvin 770, ^®Tinuvin 765, ^®Tinuvin 123, ^®Hostavin N 20, ^®Hostavin N 24, ^®Uvinul 4049, ^®Sanduvor PR 31 , ^®Uvinul 4050, ^®Good-rite UV 3034 or ^®Good-rite 3150, ^®Sanduvor 3055, ^®Sanduvor 3056, ^®Sanduvor 3058, ^®Chimassorb 1 19 and ^®Chimassorb 905. Particularly advantageous polymeric HALS stabilizers are compounds of the formulae B1 to B7:

B1

in which

R¹ is hydrogen, C₅-C₇cycloalkyl or a d-C₁₂alkyl group,

R¹³ is hydrogen or methyl,

R¹⁴ is a direct bond or d-C₁₀alkylene, and r is a number from 2 to 50;

B2

where R¹ and R⁴ are as defined above, R¹⁵ and R¹⁸ independently of one another are a direct bond or a group

-N(R²²)-CO- R²³-CO-N(R²⁴)-, R²² and R²⁴ independently of one another are hydrogen, d-C₈alkyl, C₅-C₁₂cycloalkyl, phenyl, C₇-C₉phenylalkyl or a group of the formula

R²³ is a direct bond or d-C₄alkylene,

R¹⁶, R¹⁷, R²⁰ and R²¹ independently of one another are hydrogen, d-C₃₀alkyl,

C₅-Cι₂cycloalkyl, phenyl, or a group of the formula B2a, R ⁹ is hydrogen, d-doalkyl, C₅-C₁₂cycloalkyl, C₇-C₉phenylalkyl, phenyl or a group of the formula B2a, and s is a number from 1 to 50;

B3

where

R\ R⁴ and s are as defined above, and

R²⁵, R²⁶, R²⁷, R²⁸ and R²⁹ independently of one another are a direct bond or d-doalkylene;

a product B4 obtainable by reacting a product itself obtained by reaction of a polyamine of the formula B4a with cyanuric chloride with a compound of the formula B4b, H,N (CH.) -Nh (CH₂) Nh (CH₂). NH. (B4a) n_E n

where R¹ and R⁴ are as defined above, n₅', n₅- and n₅- independently of one another are a number from 2 to 12,

_R30 is as defined above; B4 being a compound of the formula B4-1 , B4-2 or

B4-3

( B4-1 )

( B4-2 )

(B4-3)

or a mixture thereof, in which n₅ is from 1 to 20,

R⁴ and R³⁰ are as defined above;

B5

where r is as defined for formula B1 ,

R³¹, R³³ and R³⁴ independently of one another are hydrogen, d-C₁₂alkyl, C₅-C₁₂cycloalkyl, d-C₄alkyl-substituted C₅-C₁₂cycloalkyl, phenyl, -OH- and/or d-d₀alkyl- substituted phenyl, C₇-C₉phenylalkyl, C₇-C₉phenylkalyl substituted on the phenyl radical by -OH and/or d-C^alkyl, or are a group of the formula B5a

where

R¹ and R⁵ are as defined above, and

R³² is C₂-Cι₈alkylene, C₅-C₇cycloalkylene or Cι-C₄alkylenedi(C₅-C₇cycloalkylene),

or the radicals R³¹, R³² and R³³, together with the nitrogen atoms to which they are attached, form a 5- to 10-membered heterocyclic ring, and where at least one of the radicals R³ , R³³ and R³⁴ is a group of the formula B5a;

B6

in which

_R3i _R32 _R33 _{and r} are as defined above,

R³⁵ and R³⁶ independently of one another can be as defined for R ,3^J4⁴, or R³⁵ and R³⁶, together with the nitrogen atom to which they are attached, form a 5- to 10-membered heterocyclic ring which in addition to the nitrogen heteroatom may also contain one or more heteroatoms, preferably an oxygen atom, and at least one of the radicals R³¹, R³³, R³⁵ and/or R³⁶ is a group of the formula (B5a);

where

R¹ and R⁴ are as defined above, s is as defined for formula B3,

R³⁷ is d-C₁₀alkyl, C₅-C₁₂cycloalkyl, d-C₄alkyl-substituted C₅-C₁₂cycloalkyl, phenyl or

Cι-Cιoalkyl-substituted phenyl, and ,38 is C₃-C₁₀alkylene.

The compounds described as components B1 to B4 are essentially known (in some cases available commercially) and can be prepared by known processes, for example as described in US 4,233,412, US 4,340,534, US 4,857,595, DD-A-262 439 (Derwent 89-122 983/17, Chemical Abstracts 111 :58 964u), DE-A-4 239 437 (Derwent 94-177 274/22), US 4,529,760, US 4,477,615 and Chemical Abstracts - CAS No. 136 504-96-6.

Component B4 can be prepared in analogy to known processes, for example, by reacting a polyamine of the formula B4a with cyanuric chloride in a molar ratio of from 1 :2 to 1 :4 in the presence of anhydrous lithium, sodium or potassium carbonate in an organic solvent such as 1 ,2-dichloroethane, toluene, xylene, benzene, dioxane or tert-amyl alcohol at a temperature of from -20°C to +10°C, preferably from -10°C to +10°C, in particular from 0°C to +10°C, for from 2 to 8 hours and subsequently reacting the resulting product with a 2,2,6,6-tetramethyl- 4-piperidylamine of the formula B4b. The molar ratio of 2,2,6,6-tetramethyl-4-piperidylamine to polyamine of the formula B4a used is, for example, from 4:1 to 8:1. The amount of 2,2,6,6- tetramethyl-4-piperidyiamine can be added all at once or in a number of portions at intervals of several hours.

Preferably, the ratio of polyamine of the formula B4a to cyanuric chloride to 2,2,6,6- tetramethyl-4-piperidylamine of the formula B4b is from 1 :3:5 to 1 :3:6.

In general, the component B4 can be represented, for example, by a compound of the formula B4-1 , B4-2 or B4-3. It can also be present as a mixture of these three compounds.

One preferred meaning of the formula B4-1 is

One preferred meaning of the formula B4-2 is

One preferred meaning of the formula B4-3 is

Preference is given to compounds of the formulae B1 to B7 in which R¹ is hydrogen or a C C₄alkyl group, R² and R³ independently of one another are a hydrogen atom, a d-C₈alkyl group or, together with the carbon atom connecting them, are a ring with a ring size of from 6 to 12, or together with the carbon atom connecting them are a group of the formula (IV),

R⁴ and R⁵ independently of one another are either hydrogen or a d-C₅alkyl group, an oxygen radical O*, -OH, -NO, -CH₂CN, benzyl, allyl, a d-Cioalkyloxy group, a C₅-C₆cycloalkyloxy group, a C₆-C₇aryloxy group, where the aryl radical can also be substituted further, a C₇-C₁₀arylalkyloxy group, where the aryl radical can also be substituted further, a C₃-C₆alkenyl group, a C₃-C₆alkynyl group, a d-C₄acyl group, halogen, or C₇-C₉phenylalkyl which is unsubstituted or substituted on the phenyl ring by d-C₂alkyl,

R¹³ is hydrogen or methyl,

R¹⁴ is d-C₅alkylene,

R ⁷ and R² are hydrogen or d-C₄alkyl,

R¹⁵ and R¹⁸ are a direct bond,

R ⁶ and R²⁰ are d-C₂₅aikyl or phenyl,

R¹⁹ is hydrogen, d-C₁₂alkyl or a group of the formula B2a,

R²⁵, R²⁶, R²⁷, R²⁸ and R²⁹ independently of one another are a direct bond or d-C₅alkylene,

R³⁰ is hydrogen, Cι-C alkyl, C₅-C₆cycloalkyl or phenyl,

R³¹, R³³ and R³⁴ independently of one another are hydrogen, d-C₁₀alkyl,

C₅-C₆cycloalkyl or a group of the formula B5a,

R³² is C₂-C₁₀alkylene or C₅-C₆cycloalkylene,

R³⁵ and R³⁶ independently of one another are as defined for R³⁴, or R³⁵ and

R³⁶ together with the nitrogen atom to which they are attached form a 5- to 7-membered heterocyclic ring which may also contain one or more heteroatoms, preferably an oxygen atom, and at least one of the radicals R³¹, R³³, R³⁵ and/or R³⁶ is a group of the formula B5a,

R³⁷ is d-C₅alkyl, C₅-C₆cycloalkyl or phenyl,

R³⁸ C₃-C₅alkylene, and n_5',n₅',n₅- are from 2 to 4.

Very particular preference is given to compounds of the formulae B1 to B7 in which R¹ is methyl, R² and R³ together with the carbon atom connecting them are a ring with a ring size of

12, or together with the carbon atom connecting them are a group of the formula (IV),

R⁴ and R⁵ independently of one another are hydrogen, acetyl, methyl, octyloxy or cyclohexyloxy,

R ³ is hydrogen,

R¹⁴ is ethylene,

R¹⁷ and R²¹ are hydrogen or methyl,

R¹⁵ and R ⁸ are a direct bond,

R¹⁶ and R²⁰ are d-C₂₅alkyl or phenyl,

R¹⁹ is hexadecyl or a group of the formula B2a,

R²⁵ and R²⁷ are methylene,

R²⁶ is a direct bond,

R²⁸ is 2,2-dimethylethylene,

R²⁹ is 1 ,1-dimethylethylene,

R³⁰ is n-butyl,

R³¹, R³³ and R³⁴ independently of one another are isooctyl, cyclohexyi or 2,2,6,6- tetramethylpiperid-4-yl, at least one of the radicals R³¹, R³³ and R³⁴ having to be 2,2,6, 6-tetramethylpiperid-4-yl,

R³² is hexamethylene,

R³⁵ and R³⁶ independently of one another are as defined for R³⁴, or R³⁵ and R³⁶ together with the nitrogen atom to which they are attached form a 6-membered heterocyclic ring which further includes an oxygen atom and is therefore morpholine, at least one of the radicals R³¹, R³³, R³⁵ and/or R³⁶ having to be a 2,2,6,6-tetramethylpiperid-4-yl radical,

R³⁷ is methyl,

R³⁸ is trimethylene, n₅',n₅",n_5" are from 2 to 4.

With very particular preference, the polymeric HALS compounds comprise the following substances:

B' 2

O C CH,

CCH-CH - CHCH₂CO CH₂C CCH₂0

C^{: :}0 CH, CH,

CH, CH, ₂0

o - B'5

B'6

B'7

B'8

CH,

H₃C Si H

C H.

CH,

B' 9

C H,

a product B'10 obtainable by reacting a product itself obtained by reaction of a polyamine of the formula B'10a:

H2N-(CH₂)₃-NH-(CH₂)2-NH-(CH2)₃-NH2 (B'10a)

with cyanuric chloride with a compound of the formula (B'10b)

where B'10 is a compound of the formula B4-1', B4-2' or B4-3'

or a mixture thereof, where n₅ is from 1 to 20.

Particular preference is given to ^®Chimassorb 944, ^®Tinuvin 622, ^®Dastib 1082, ^®Uvasorb HA 88, ^®Uvinul 5050, ^®Lowilite 62, ^®Uvasil 299, ^®Cyasorb 3346, ^®MARK LA 63, ^®MARK LA 68 or ^®Luchem B 18.

Also suitable are combinations of polymeric HALS stabilizers, as described, for example, in EP-A-252877, EP-A-709426, Research Disclosure Jan. 1993, No. 34549 and EP-A-723990.

Suitable organophosphites and organophosphonites are compounds of the formulae C1 to C7:

OR',

OR',

RVY'-P, C1 A' X'-P C2

OR', OR', n'

in which the indices are integral and n' is 2, 3 or 4; u is 1 or 2; t is 2 or 3; y is 1 , 2 or 3; and z is from 1 to 6; A', if n' is 2, is alkylene having 2 to 18 carbon atoms; -S-, -O- or -NR'₄-interrupted alkylene having 2 to 12 carbon atoms; a radical of one of the formulae

or phenylene;

A', if n' is 3, is a radical of the formula -C_rH_2r-ι;

A', if n' is 4, is the radical of the formula C(CH₂)₄-;

A" is as defined for A' if n' is 2;

B' is a radical of the formula -CH₂-; -CHR'₄-; -CR'_TR ; -S- or a direct bond; or is

C₅-C₇cycloalkylidene; or is cyclohexylidene substituted by from 1 to 4 C₁-C₄alkyl radicals in positions 3, 4 and/or 5, D', if u is 1 , is methyl and, if u is 2, is -CH₂OCH₂-;

E', if y is 1 , is alkyl having 1 to 18 carbon atoms, phenyl, a radical of the formula -OR¹! or halogen; E', if y is 2, is a radical of the formula -O-A"-O-; E', if y is 3, is a radical of the formula R'₄C(CH₂O)₃- or N(CH₂-CH₂-O-)₃; Q' is the radical of an at least z-hydric alcohol or phenol and is attached to the phosphorus atom(s) by way of the alcoholic or phenolic oxygen atom(s) respectively;

R'ι, R'₂ and R'₃ independently of one another are alkyl having 1 to 30 carbon atoms; halogen-, -COORV, -CN- or -CONR'₄R'₄-substituted alkyl having 1 to 18 carbon atoms; -S-, -O- or -NR'₄-interrupted alkyl having 2 to 18 carbon atoms; phenyl-d-C alkyl; cycloalkyl having 5 to 12 carbon atoms; phenyl or naphthyl; phenyl or naphthyl substituted by halogen, by from 1 to 3 alkyl radicals or alkoxy radicals having in total 1 to 18 carbon atoms or by phenyl-C₁-C₄alkyi; or a radical of the formula

in which w is an integer from 3 to 6;

R'₄ or the radicals R'₄ independently of one another is or are hydrogen, alkyl having 1 to 18 carbon atoms, cycloalkyl having 5 to 12 carbon atoms or phenylalkyl having 1 to 4 carbon atoms in the alkyl moiety;

R's and R'₆ independently of one another are hydrogen, alkyl having 1 to 8 carbon atoms or cycloalkyl having 5 or 6 carbon atoms;

R'₇ and R'₈ if t = 2 are independently of one another Cι-C₄alkyl or together are a

2,3-dehydropentamethylene radical; and

R'₇ and R'₈ if t = 3 are methyl; the substituents R'₁ independently of one another are hydrogen, alkyl having 1 to 9 carbon atoms or cyclohexyi; the substituents R'₁ independently of one another are hydrogen or methyl, and

R'₁₆ is hydrogen or C C alkyl and, if two or more radicals R'₁₆ are present, the radicals R'₁₆ are identical or different; X' and Y' are each a direct bond or -O-; and Z is a direct bond; -CH₂-; -C(R'ι₆)₂- or -S-.

Particular preference is given to phosphites or phosphonites of the formulae C1 , C2, C5 or C6 in which

n' is 2 and y is 1 or 2;

A' is alkylene having 2 to 18 carbon atoms; p-phenyiene or p-biphenylene; E' if y = 1 is CτCι₈alkyl, -OR_T or fluorine; and if y = 2 is p-biphenylene;

R'_L R'₂ and R'₃ independently of one another are alkyl having 1 to 18 carbon atoms; phenyl-d-C₄alkyl; cyclohexyi; phenyl; or phenyl substituted by from 1 to 3 alkyl radicals having in total 1 to 18 carbon atoms; the substituents R'₁ independently of one another are hydrogen or alkyl having 1 to 9 carbon atoms; R'15 is hydrogen or methyl;

X' is a direct bond;

Y" is -O-; and

71 is a direct bond or -CH(R'₁₆)-.

Very particular preference is given to phosphites or phosphonites of one of the formulae C1 , C2, C5 or C6 in which

n' is 2 and y is 1;

A' is p-biphenylene;

E' is d-Ciβalkoxy;

R'ι, R'₂ and R'₃ independently of one another are phenyl substituted by 2 or 3 alkyl radicals having in total 2 to 12 carbon atoms; the substituents R' independently of one another are methyl or tert-butyl;

R'15 is hydrogen;

X' is a direct bond;

Y' is -O-; and

Z' is a direct bond, -CH₂- or -CH(CH₃)-.

In particular, the specific phosphorus compounds of the formula C'1 to C'12 are to be mentioned:

In the formula C'3 the two phosphorus substituents are predominantly in positions 4 and 4' of the biphenyl parent structure

C 6

C' 7

C'8

C'10

C'11

The abovementioned phosphites and phosphonites are known compounds and some of them are available commercially.

The following stabilizer mixtures comprise particularly suitable embodiments of the invention:

Compound I and ^®lrgafos 38, Compound I and ^®lrgafos 12, Compound I and ^®Hostanox PAR 24, Compound I and ^®Hostanox OSP 1 , Compound I and ^®Sandostab P-EPQ,

Compound I and ^®Ultranox 626,

Compound I and ^®Ultranox 618,

Compound I and ^®Mark PEP-36 (from Asahi Denka),

Compound I and ^®Mark HP10 (from Asahi Denka),

Compound I and ^®Doverphos 9228

The combination of compounds (I) with phosphites and phosphonites is also outstandingly suitable in the sense that the phosphite and/or phosphonite synergistically supports the action of the compounds (I) in stabilizing organic material. Synergistic effects of this kind are described in EP-A-359276 and EP-A-567117. Particularly suitable mixtures are those of compounds (I) with phosphites and/or phosphonites of the formulae C'1 to C'12.

The compounds (I) are also outstandingly suitable for combination with phosphite and/or phosphonite, and/or a sterically hindered phenol and/or an acid scavenger. A particularly suitable combination is that of the compounds (I) in mixtures with phosphite and/or phosphonite, phenol and acid scavenger, in a manner as described by DE-A-19537140.

The compounds (I) and the mixtures described above are also suitable for combination with other stabilizers, especially light stabilizers, such as those, for example, from the class of the UV absorbers (2-hydroxybenzophenones or 2-hydroxyphenylbenzotriazoles, cinnamic acid derivatives, oxaniiides) and/or nickel quenchers in a synergistic manner.

In the mixtures described above, the proportion of compounds of the formula (I) can be between 1 and 99% by weight.

The compounds (I) are also suitable for use in combination with zeolites or hydrotalcites, such as ^®DHT4A in analogy to EP-A-429731.

The compounds (I) and the mixtures described above can also be combined with one or more N,N-dialkyl-substituted hydroxylamines, preferably with N.N-dioctadecylhydroxylamine.

Furthermore, the compounds (I) can be combined with one or more basic or other acid- binding costabilizers from the group of the metal carboxylates, metal oxides, metal hydroxides, metal carbonates, and/or zeolites, and/or hydrotalcites. Preferred costabilizers are calcium stearate, and/or magnesium stearate, and/or magnesium oxide, and/or zinc oxide, and/or zinc oxide containing carbonate, and/or hydrotalcite.

Particularly preferred costabilizers are ^®Zinkoxid aktiv, ^®Zinkoxid transparent and/or one of the hydrotalcites ^®DHT 4A, ^®DHT4 A2, ^® Kyowaad 200, ^®Kyowaad 300, ^®Kyowaad 400, ^®Kyowaad 500, ^®Kyowaad 600, ^®Kyowaad 700, ^®Kyowaad 1000 and ^®Kyowaad 2000.

In accordance with the invention, the compounds of the formula I alone or in combinations with other stabilizers are used to stabilize plastics substrates or plastic-coated substrates during their production and processing.

Examples of such materials are:

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poiy-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for example of cyclopentene or norbornene; furthermore polyethylene (which optionally can be crosslinked); for example, high density polyethylene (HDPE), polyethylene of high density and high molar mass (HDPE-HMW), polyethylene of high density and ultrahigh molar mass (HDPE-UHMW), medium density polyethylene (HMDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).

Polyolefins, i.e. polymers of monoolefins exemplified in the preceding paragraph, in particular polyethylene and polypropylene, can be prepared by various, and especially by the following, methods:

a) free-radical polymerization (normally under high pressure and at elevated temperature)

b) catalytic polymerization using a catalyst that normally contains one or more metals of group IVb, Vb, Vlb or VIM of the Periodic Table. These metals usually have one or more ligands, such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either π- or σ-coordinated. These metal complexes may be in the free form or fixed on substrates, for example on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalysts can be active as such in the polymerization or further activators may be used, for example metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, the metals being elements of groups la, Ha and/or Ilia of the Periodic Table. The activators may be modified, for example, with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

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

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene-but-1-ene copolymers, propyiene-isobutylene copolymers, ethylene-but-1-ene copolymers, ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutyiene-isoprene copolymers, ethylenealkyl acrylate copolymers, ethylenealkyl methacrylate copolymers, ethylene-vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene-acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned under 1), for example poiypropylene-ethylene- propylene copolymers, LDPE-ethylene-vinyl acetate copolymers, LDPE-ethylene- acrylic acid copolymers, LLDPE-ethylene-vinyl acetate copolymers, LLDPE-ethylene- acrylic acid copolymers and alternating or random polyalkyiene-carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenated modifications thereof (e.g. tackifier resins) and mixtures of polyalkylenes and starch.

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

6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, for example styrene-butadiene, styrene-acrylonitrile, styrenealkyl methacrylate, styrene- butadienealkyl acrylate, styrene-butadienealkyl methacrylate, styrene-maleic anhydride, styrene-acrylonithle-methacrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; and block copolymers of styrene, such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene/butylene- styrene or styrene-ethylene/propylene-styrene.

7. Graft copolymers of styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyalkyl acrylates or polyalkyi methacrylates, styrene and acrylonitrile on acrylate-butadiene copolymers, as well as mixtures thereof with the copolymers mentioned under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.

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

9. Polymers derived from α,β-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates, polyacryionitriles, polyacrylamides and polymethyl methacrylates impact-modified with butyl acrylate.

10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile-butadiene copolymers, acrylonithlealkyl acrylate copolymers, acrylonitrilealkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrilealkyl methacrylate-butadiene terpolymers. 11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in section 1.

12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisgiycidyl ethers.

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

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

15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters and polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, 6, 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, 11 and 12, aromatic polyamides starting from m-xylene, diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic and/or terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthaiamide. Block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. As well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyether imides, polyester amides, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates, as well as block polyether esters derived from hydroxyl-terminated polyethers; and also 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 the one hand and phenols, urea or melamine on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with poiyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, for example from epoxy acrylates, urethane acrylates or polyester acrylates.

25. alkyd resins, polyester resins and acrylic 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, examples being products of bisphenol A diglycidyl ethers, bisphenol F diglycidyl ethers, which are crosslinked by means of customary hardeners, such as anhydrides or amines, for example, with or without accelerators.

27. Natural polymers such as cellulose, natural rubber, gelatin and derivatives thereof which have been chemically modified in a polymer-homologous manner, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and derivatives.

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

29. Natural and synthetic organic substances which constitute pure monomeric compounds or mixtures thereof, examples being mineral oils, animal or vegetable fats, oils and waxes, or oils, waxes and fats based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates), and also blends of synthetic esters with mineral oils in any desired proportion by weight, as are employed, for example, as spin finishes, and aqueous emulsions thereof.

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

The organic material stabilized by the compounds of the formula (I) of the invention or by an appropriate combination comprising this compound may if desired also comprise further additives, examples being antioxidants, light stabilizers, metal deactivators, antistatic agents, flame retardants, lubricants, nucleating agents, acid scavengers (basic costabilizers), pigments and fillers. Antioxidants and light stabilizers which are added in addition to the compounds or combinations of the invention are, for example, compounds based on sterically hindered amines or on sterically hindered phenols, or sulfur- or phosphorus- containing costabilizers. Examples of suitable additives which can additionally be employed in combination are compounds as set out below:

1. Antioxidants

1.1. alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6- dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di- tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyciohexyl)- 4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di- tert-butyl-4-methoxymethylphenol, linear or sidechain-branched nonylphenols, such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 -methylundec-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, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4- dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6- didodecylthiomethyl-4-nonylphenol. 1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-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-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Hydroxylated thiodiphenyl ethers, for example 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-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4- hydroxyphenyl) disulfide.

1.5 alkylidenebisphenols, for example 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-6cyclohexylphenol), 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-nonyiphenol], 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-hydroxybenzyl)-4-methylphenol, 1 , 1 ,3-ths(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1 , 1 -bis(5-tert-butyl-4-hydroxy- 2-methylphenyl)-3-n-dodecyimercaptobutane, bis(3-tert-butyl-4-hydroxy-5- methylphenyi)-dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methyibenzyl)-6-tert- butyl-4-methylphenyl] terephthalate, 1 ,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2- bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2- methylphenyl)-4-n-dodecylmercaptobutane, 1 ,1 ,5,5-tetra-(5-tert-butyl-4-hydroxy-2- methylphenyl)pentane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'- hydroxyphenyl)butyrate].

1.6. O-, N- and S-benzyl compounds, for example 3,5,3', 5'-tetra-tert-butyl-4,4'- dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, 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, tridecyl 4-hydroxy-3,5-di- tert-butylbenzylmercaptoacetate. 1.7. Hydroxybenzylated malonates, for example dioctadecyl 2,2-bis(3,5-di-tert-butyl-2- hydroxybenzyl)malonate, dioctadecyl 2-(3-tert-butyl-4-hydroxy-5- methylbenzyl)malonate, didodecyl mercaptoethyl-2,2-bis(3,5-di-tert-butyl-4- hydroxybenzyl)malonate, di-[4-(1 ,1 ,3,3-tetramethylbutyl)phenyl] 2,2-bis(3,5-di-tert- butyl-4-hydroxybenzyl)malonate.

1.8. Aromatic hydroxybenzyl compounds, for example 1 ,3,5-tris(3,5-di-tert-butyl-4- hydroxybenzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)- 2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.9. Thazine compounds, for example 2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4- hydroxyanilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4- hydroxyanilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4- hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3- triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl- 3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4- hydroxyphenylethyl)-1 ,3,5-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4- hydroxyphenylpropionyl)hexahydro-1 ,3,5-triazine, 1 ,3,5-tris(3,5-dicyclohexyl-4- hydroxybenzyl) isocyanurate.

1.10. benzylphosphonates, for example dimethyl 2,5-di-tert-butyl-4- hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4- hydroxy-3-methylbenzyiphosphonate, the Ca salt of the monoethyl ester of 3,5-di-tert- butyl-4-hydroxybenzylphosphonic acid.

1.11. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.12. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, isooctanol, 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)oxalamide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1- phospha-2,6,7-thoxabicyclo[2.2.2]octane. 1.13. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, isooctanol, 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)oxalamide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1- phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, isooctanol, 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)oxalamide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1- phospha-2,6,7-thoxabicyclo[2.2.2]octane.

1.15. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, isooctanol, 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)oxalamide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1- phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,3-bis(3'tert-butyl-4'-hydroxyphenyl)butyric acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, isooctanol, 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)oxalamide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1- phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, e.g. N,N'-bis(3,5-di-tert- butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl-4- hydroxyphenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl-4- hydroxyphenyipropionyl)hydrazine. 1.18. Tocopheroi, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

1.19. Ascorbic acid (vitamin C).

1.20. Amine antioxidants, for example N.N'-diisopropyl-p-phenylenediamine, N,N'-di-sec- butyi-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p-phenylenediamine, N,N'- bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p- phenyienediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p- phenylenediamine, N,N'-di(naphthyl-2-)-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-(-toluenesulfonamido)diphenylamine, N,N'-dimethyl-N,N'-di-sec- butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4- isopropoxydiphenylamine, Nphenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1- naphthylamine, Nphenyl-2-naphthylamine, octylated diphenylamine, e.g. p,p'-di-tert- octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4- nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di(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-di-[(2-methylphenyl)amino]ethane, 1 ,2-di- (phenylamino)propane, (o-tolyl)biguanide, di[4-(1',3'-dimethylbutyl)phenyl]amine, tert- octylated Nphenyl-1-naphthylamine, mixture of mono- and dialkylated tert-butyl/tert- octyldiphenylamines, mixture of mono- and dialkylated nonyldiphenylamines, mixture of mono- and dialkylated dodecyldiphenylamines, mixture of mono- and dialkylated isopropyl/isohexyl-diphenylamines, mixture of mono- and dialkylated tert- butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1 ,4-benzothiazine, phenothiazine, mixture of mono- and dialkylated tert-butyl/tert-octylphenothiazines, mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-

1 ,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethylpiperidin-4- yl)hexamethylenediamine, bis(2,2,6,6-tetramethylpiperidin-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)benzotriazoles, for example 2-(2'-hydroxy-5'- methylphenyl)benzotriazole, 2-(3',5^,-di-tert-butyl-2^,-hydroxyphenyl)benzotriazole, 2-(5'- tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1 ,1 ,3,3- tetramethylbutyl)phenyl]benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5- chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5^,-methylphenyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'- octoxyphenyi)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2- (3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, a mixture of 2-(3'-tert- butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert- butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert- butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2- (2-ethylhexyloxy)carbonyiethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'- hydroxy-5'-methylphenyl)benzotriazole, and 2-(3'-tert-butyl-2'-hydroxy-5'-(2- isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylenebis[4-(1 ,1 ,3,3- tetramethylbutyl)-6-benzotriazol-2-ylphenol]; the transesterification product of 2-[3'-tert.- butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]benzotriazole with polyethylene glycol 300; [R-CH₂CH₂-COO(CH₂)₃]2 where R = 3'-tert-butyl-4'-hydroxy-5'-2H- benzotriazol-2-ylphenyl.

2.2 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4- decyloxy, 4-dodecyloxy, 4-benzyioxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivative.

2.3 Esters of substituted or unsubstituted benzoic acids, for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert- butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4- hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert- butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4- hydroxybenzoate.

2.4 Acrylates, for example ethyl αcyano-β,β-diphenylacrylate or isooctyl αcyano-β,β- diphenylacrylate, methyl α-carbomethoxycinnamate, methyl αcyano-β-methyl-p- methoxycinnamate or butyl αcyano-β-methyl-p-methoxycinnamate, methyl α- carbomethoxy-p-methoxycinnamate and N-(β-carbomethoxy-βcyanovinyl)-2- methylindoline. 2.5 Nickel compounds, for example nickel complexes of 2,2'-thio-bis-[4-(1 ,1 ,3,3- tetramethylbutyl)phenol], such as the 1 :1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, such as of the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzyiphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecyl ketoxime, nickel complexes of

1 phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.

2.6 Sterically hindered amines, for example bis(2,2,6,6-tetramethylpipehdin-4-yl) sebacate, bis(2,2,6,6-tetramethylpiperidin-4-yl) glutarate, bis(2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis(1 ,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, bis(1 ,2,2,6,6- pentamethylpipehdin-4-yl) glutarate, 2,2,6,6-tetramethylpipehdyl behenate, 1 ,2,2,6,6- pentamethylpiperidyl behenate, the condensate of 1-hydroxyethyl-2,2,6,6-tetramethyl- 4-hydroxypiperidine and succinic acid, the condensate of N,N'-bis-(2,2,6,6-tetramethyl- 4-pipehdyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1 ,3,5-s-thazine, tris-(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4- piperidyl) 1 ,2,3,4-butantetraoate, 1 ,1'-(1 ,2-ethanediyl)-bis-(3,3,5,5- tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6- tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-

1 , 2,2,6, 6-pentamethylpiperidine, 4-stearoyloxy-1 ,2,2,6,6-pentamethylpiperidine, bis(1 ,2,2,6,6-pentamethylpiperidyl) 2-n-butyl-2-(2-hydroxy-3,5-di-tert- butylbenzyl)malonate, bis(1 ,2,2,6,6-pentamethylpiperidyl) 2-n-butyl-2-(4-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- tetramethylpiperidyl) succinate, the condensate of N,N'-bis(2,2,6,6-tetramethyl-4- piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1 ,3,5-triazine, the condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4cyclohexylamino-2,6-dichloro-1 ,3,5-triazine, the condensate of 2-chloro-4,6-di-(4-n- butylamino-2,2,6,6-tetramethylpiperidyl)-1 ,3,5-triazine and 1 ,2-bis-(3- aminopropyiamino)ethane, the condensate of 2-chloro-4,6-di-(4-methoxypropylamino- 2,2,6,6-tetramethylpiperidyl)-1 ,3,5-triazine and 1 ,2-bis-(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-methoxypropylamino-1 ,2,2,6,6- pentamethylpiperidyl)-1 ,3,5-triazine and 1 ,2-bis-(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1 ,2,2,6,6-pentamethylpiperidyl)-1 ,3,5- triazine and 1 ,2-bis-(3-aminopropylamino)-ethane, reaction products of 2-chloro-4,6-di- (4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1 ,3,5-triazine with mono- or polyfunctional amines, where between one and all the active hydrogen atoms on the amine are replaced, such as with ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, 1 ,2-bis-(3-aminopropylamino)ethane, reaction products of 2- chloro-4,6-di-(4-n-butylamino-1 ,2,2,6,6-pentamethylpiperidyl)-1 ,3,5-triazine with mono- or polyfunctional amines, where between one and all the active hydrogen atoms on the amine are replaced, such as with ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, 1 ,2-bis(3-aminopropylamino)ethane, reaction products of 2-chloro-4,6-di-(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1 ,3,5- triazine and 4-tert-octylamino-2,6-dichloro-1 ,3,5-s-triazine with mono- or polyfunctional amines, where between one and all the active hydrogen atoms on the amine are replaced, such as with ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, 1 ,2-bis(3-aminopropylamino)ethane, reaction products of 2- chloro-4,6-di-(4-n-butylamino-1 ,2,2,6,6-pentamethylpiperidyl)-1 ,3,5-triazine and 4-tert- octylamino-2,6-dichloro-1 ,3,5-s-triazine with mono- or polyfunctional amines, where between one and all the active hydrogen atoms on the amine are replaced, such as with ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, 1 ,2-bis-(3-aminopropyl-amino)ethane, reaction products of 2-chloro-4,6-di-(4-n- butylamino-2,2,6,6-tetramethylpiperidyl)-1 ,3,5-triazine and 4-(4-n-butylamino-2,2,6,6- tetramethylpiperidyl)-2,6-dichloro-1,3,5-s-triazine with mono- or polyfunctional amines, where between one and all the active hydrogen atoms on the amine are replaced, such as with ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, 1 ,2-bis-(3-aminopropylamino)ethane, reaction products of 2- chloro-4,6-di-(4-n-butylamino-1 ,2,2,6,6-pentamethyipiperidyl)-1 ,3,5-triazine and 4-(4-n- butylamino-2,2,6,6-tetramethylpiperidyl)-2,6-dichloro-1 ,3,5-s-triazine with mono- or polyfunctional amines, where between one and all the active hydrogen atoms on the amine are replaced, such as with ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, 1 ,2-bis-(3-aminopropylamino)ethane, the condensate of 1 ,2-bis(3-aminopropylamino)ethane and 2,4,6-trichioro-1 ,3,5-triazine and also 4-butylamino-2,2,6,6-tetramethylpiperidine, N-(2,2,6,6-tetramethyl-4- piperidyl)-n-dodecylsuccinimide, N-(1 ,2,2,6,6-pentamethyl-4-pipehdyl)-n- dodecylsuccinimide, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1 ,3,8- triazaspiro[4.5]decane-2,4-dione, oligomerized 2,2,4,4-tetramethyl-20-(oxiranylmethyl)- 7-oxa-3,20-diaza-dispiro[5.1.11.2]heneicosan-21-one, oligomerized 1 ,2,2,4,4- pentamethyl-20-(oxiranylmethyl)-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one, oligomerized 1-acetyl-2,2,4,4-tetramethyl-20-(oxiranylmethyl)-7-oxa-3,20-diaza- dispiro[5.1.11.2]heneicosan-21 -one, 3-dodecyl-1 -(2,2,6,6-tetramethyl-4- pipehdyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1 ,2,2,6,6-pentamethyl-4- piperidyl)pyrrolidine-2,5-dione, 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro- [5.1.11.2]heneicosan-21-one, 2,2,4,4-tetramethyl-7-oxa-21-oxo-3,20-diazadispiro- [5.1.11.2]heneicosane-3-propanoic acid dodecyl ester, 2,2,4,4-tetramethyl-7-oxa-21- oxo-3, 20-diazadispiro-[5.1.11.2]heneicosane-3-propanoic acid tetradecyl ester, 2,2,3,4,4-pentamethyl-7-oxa-3,20-diazadispiro-[5.1.11.2]heneicosan-21-one, 2,2,3,4,4- pentamethyl-7-oxa-21 -oxo-3,20-diaza-dispiro-[5.1.11.2]heneicosane-3-propanoic acid dodecyl ester, 2,2,3,4,4-pentamethyl-7-oxa-21-oxo-3,20-diazadispiro-[5.1.11.2]- heneicosane-3-propanoic acid tetradecyl ester, 3-acetyl-2,2,4,4-tetramethyl-7-oxa- 3,20-diazadispiro-[5.1.11.2]heneicosane-21-one, 3-acetyl-2,2,4,4-tetramethyl-7-oxa-21- oxo-3, 20-diaza-dispiro-[5.1.11.2]heneicosane-3-propanoic acid dodecyl ester, 3-acetyl- 2,2,4,4-tetramethyl-7-oxa-21 -oxo-3,20-diazadispiro-[5.1.11.2]heneicosane-3-propanoic acid tetradecyl ester, l .l'.S.S'.δ.S'-hexahydro^ A^.e.e'-hexaaza^ .e.e'- bismethano-7,8-dioxo-4,4'-bis(1 ,2,2,6,6-pentamethyl-4-piperidyl)biphenyl, poly-N,N'- bis-(2,2,6,6-tetramethyl-4-pipehdyl)-1,8-diazadecylene, adduct of 2,2,6,6-tetramethyl-4- allyloxypiperidine and polymethylhydridosiloxane (molar mass up to 4000), adduct of 1 ,2,2,6,6-pentamethyl-4-allyloxypiperidine and polymethylhydridosiloxane (molar mass up to 4000), N,N'-diformyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)- hexamethylenediamine, N,N'-diformyl-N,N'-bis(1 ,2,2,6,6-pentamethyl-4- piperidinyl)hexamethylenediamine, 5,11-bis-(2,2,6,6-tetramethyl-4-piperidinyl)- 3,5,7,9,11 ,13-hexaazatetracyclo[7.4.0.0²'⁷.1³'¹³]tetradecane-8,14-dione, 5,11- bis(1 ,2,2,6,6-pentamethyl-4-piperidinyl)-3,5,7,9,11 ,13- hexaazatetracyclo[7.4.0.0^2,7.1^{3 13}]tetradecane-8,14-dione, [(4- methoxyphenyl)methylene]-propanedioic acid bis(2,2,6,6-tetramethyl-4-piperidinyl) ester, [(4-methoxyphenyl)-methylene]propanedioic acid bis-(1, 2,2,6, 6-pentamethyl-4- piperidinyl) ester, 2,4,6-tris(N-cyclohexyl-N-[2-(3,3,4,5,5-pentamethylpiperazinon-1 - yl)ethyl]amino)-1 ,3,5-triazine, copolymer of styrene with methylstyrene and maleic anhydride reacted with 4-amino-2,2,6,6-tetramethylpiperidine and octadecylamine, copolymer of styrene with α-methylstyrene and maleic anhydride reacted with 4-amino- 1 ,2,2,6,6-pentamethylpiperidine and octadecylamine, polycarbonate with 2,2'-[(2,2,6,6- tetramethyl-4-piperidinyl)imino]bis[ethanol] as diol component, polycarbonate comprising 2,2'-(1,2,2,6,6-pentamethyl-4-piperidinyl)imino]bis[ethanol] as diol component, copolymer of maleic anhydride and an α-olefin up to C₃₀ reacted with 4- amino-2,2,6,6-tetramethylpiperidine, copolymer of maleic anhydride and an α-olefin up to C₃₀ reacted with 1-acetyl-4-amino-2,2,6,6-tetramethylpiperidine, copolymer of maleic anhydride and an α-olefin up to C₃₀ reacted with 4-amino-1 ,2,2,6,6- pentamethylpiperidine, and also the N-alkyl- and N-aryl-oxy derivatives of the abovementioned compounds with free NH groups on the piperidine, especially α- methylbenzyloxy and alkyloxy from d to Ci8. 2.7 Oxalamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide, 2-ethoxy-2'- ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)-oxalamide, 2-ethoxy-5-tert-butyl-2'- ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of o- and p-methoxy-disubstituted and of o- and p-ethoxy-disubstituted oxanilides.

2.8 2-(2-Hydroxyphenyl)-1 ,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4- octyloxyphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4',6-bis(2',4- dimethylphenyl)-1 ,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-

1 ,3,5-triazine, 2-(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)-4,6bis(4-methylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4- dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-thazine, 2-[2-hydroxy-4-(2- hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-[2- hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1 ,3,5- triazine, 2-(2-hydroxy-4-thdecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2- [4-dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4- dimethylphenyl)-1 ,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3- dodecyloxypropoxy)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-thazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]- 1 ,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6phenyl-1 ,3,5-triazine.

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

4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, ths(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, bisisodecyloxy pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6- methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, thstearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'- biphenyienediphosphonite, 6-isooctyloxy-2,4,8, 10-tetra-tert-butyl-12H-dibenzo[d,g]- 1 ,3,2-dioxaphosphocin, 6-fluoro-2,4,8, 10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1 ,3,2- dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis(2,4-di-tert- butyl-6-methylphenyl) ethyl phosphite, tris(2-tert-butyl-4-thio(2'-methyl-4'-hydroxy-5'- tert-butyl)phenyl-5-methyl) phenyl phosphite, 2,2',2"-nitrilo[triethyl tris(3,3',5,5'-tetra-tert- butyl-1 ,1'-biphenyl-2,2'-diyl) phosphite], bis[2-methyl-4,6-bis(1 ,1- dimethylethyl)phenol]phosphorous acid ethyl ester.

5. Hydroxylamines, examples being N,N-dibenzylhydroxylamine, N,N- diethylhydroxylamine, N,N-dioctyihydroxylamine, N,N-dilaurylhydroxylamine, N,N- ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N- dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N- octadecylhydroxyiamine, N,N-dialkylhydroxylamines prepared from hydrogenated tallow fatty amine.

6. Nitrones, examples being N-benzyl alphaphenyl nitrone, N-ethyl alpha-methyl nitrone, N-octyl alpha-heptyl nitrone, N-lauryl alpha-undecyl nitrone, N-tetradecyl alpha-tridecyl nitrone, N-hexadecyl alpha-pentadecyl nitrone, N-octadecyl alpha-heptadecyl nitrone, N-hexadecyl alpha-heptadecyl nitrone, N-octadecyl alpha-pentadecyl nitrone, N- heptadecyl alpha-heptadecyl nitrone, N-octadecyl alpha-hexadecyl nitrone, nitrones derived from N,N-diaikylhydroxylamines prepared from hydrogenated tallow fatty amines.

7. Zeolites and hydrotalcites, such as ^®DHT 4A. Hydrotalcites of this kind can be described by the formula

[(M²⁺)_1-x (M³⁺)_x (OH)₂ ^n' yH₂O],

where

(M²⁺) is Mg, Ca, Sr, Ba, Zn, Pb, Sn, Ni

(M³⁺) is Al, B, Bi

Aⁿ is an anion of valency n n is an integer from 1 - 4 x is a value between 0 and 0.5 y is a value between 0 and 2

A is OH^", CI^', Br^", I^", CIO₄-, CH₃COO\ C₆H₅COO-, CO₃ ^2", SO₄ ²\ (OOC-COO)²-, (CHOHCOO)₂ ^2', (CHOH)₄CH₂OHCOO^", C₂H₄(COO)₂ ^2", (CH₂COO)₂ ^2', CH₃CHOHCOO^", SiO₃ ^2", SiO₄ ^4', Fe(CN)₆ ^3", Fe(CN)₆ ⁴-, BO₃ ^3", PO₃ ^3", HPO₄ ^2".

Preference is given to employing hydrotalcites in which (M²⁺) is (Ca²⁺), (Mg²⁺) or a mixture of (Mg²⁺) and (Zn²⁺); (A^n") is CO₃ ^2', BO₃ ^3", PO₃ ^3"; x has a value from 0 to 0.5 and y has a value from 0 to 2. It is also possible to employ hydrotalcites that can be described with the formula

[(M²⁺)_x (AI³⁺)₂ (OH)_2x+6nz (A^n")₂ yH₂0].

Here, (M²⁺) is Mg²⁺, Zn²⁺, but more preferably Mg²⁺. (A^n") is an anion, in particular from the group consisting of CO₃ ^2', (OOC-COO)^2", OH^" and S^2', where n describes the valency of the ion. y is a positive number, more preferably between 0 and 5, especially between 0.5 and 5. x and z have positive values, which in the case of x are preferably between 2 and 6 and in the case of z should be less than 2. The hydrotalcites of the following formulae are to be regarded with particular preference:

AI₂O₃ x 6MgO x CO₂ x 12H₂O , Mg_{4 5}AI₂(OH)ι₃ x CO₃ x 3.5H₂O , 4MgO x AI₂O₃ x CO₂ x 9H₂O , 4MgO x AI₂O₃ x CO₂ x 6H₂O , ZnO x 3MgO x AI₂O₃ x CO₂ x 8-9H₂O , ZnO x 3MgO x AI₂O₃ x CO₂ x 5-6H₂O , Mg_{4 5}AI₂(OH)₁₃ x CO₃ .

Hydrotalcites are employed in the polymer preferably in a concentration of from 0.01 to 5 % by weight, in particular from 0.2 to 3 % by weight, based on the overall polymer formulation.

8. Thiosynergists, examples being dilauryl thiodipropionate and distearyl thiodipropionate.

9. Peroxide scavengers, examples being esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mecaptobenzimidazole, the zinc salt of 2- mercaptobenzimidazole, zinc alkyldithiocarbama.es, zinc dibutyldithiocarbamate, dioctadecyl monosulfide, dioctadecyl disulfide, pentaerythritol tetrakis(β- dodecylmercapto)propionate.

10. Polyamide stabilizers, examples being copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.

11. Basic costabilizers, examples being melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamines, polyurethanes, alkali metal and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg behenate, Mg stearate, Na ricinoleate, K palmitate, antimony pyrocatecholate or tin pyrocatechoiate, alkali metal and alkaline earth metal salts and also the zinc salt or the aluminium salt of lactic acid.

12. Nucleating agents, such as inorganic substances, examples being talc, metal oxides, such as titanium oxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals, organic compounds, such as mono- or polycarboxylic acids and also their salts, examples being 4-tert-butylbenzoic acid, adipic acid; diphenylacetic acid; sodium succinate or sodium benzoate; acetals of aromatic aldehydes and polyfunctional alcohols such as sorbitol, for example, such as 1 ,3-2,4- di(benzylidene)-D-sorbitol, 1 ,3-2,4-di(4-tolylidene)-D-sorbitol, 1 ,3-2,4-di(4- ethylbenzylidene)-D-sorbitol, polymeric compounds, such as ionic copolymers (ionomers), for example.

13. Fillers and reinforcing agents, examples being calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and metal hydroxides, carbon black, graphite, wood flour and other flours or fibers of other natural products, synthetic fibers.

14. Other additives, examples being plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, levelling assistants, optical brighteners, flameproofing agents, antistatics, blowing agents.

The additives of the general formula (I) or the combinations described are incorporated into the organic material, preferably into the polymer, by the customary methods. Incorporation can take place, for example, by mixing or applying the compounds and any other additives into or onto the polymer directly before, during or after the polymerization or into the polymer melt before or during shaping. Incorporation can also be effected by applying the dissolved or dispersed compounds to the polymer directly or by mixing them into a solution, suspension or emulsion of the polymer, with or without subsequent evaporation of the solvent. The compounds are also effective if they are incorporated subsequently, in a separate processing step, into a polymer which has already been granulated. The compounds of the formula (I) can also be added in the form of a masterbatch containing these compounds, for example, in a concentration of from 1 to 75, preferably from 2.5 to 30, % by weight, to the polymers to be stabilized.

The examples below are intended to illustrate the invention without restricting it in any way.

TABLE 1

Overview of benzofuranone compounds:

Compounds 1 1 to 2 8 correspond to the formula I, compounds 3 1 to 3 5 are comparison substances with alkyl substitution in position 4

EXAMPLE 1

100 parts of polypropylene powder, type Eltex P HL 001 PF (manufacturer Solvay Polyolefines) are mixed together with 10 or 20 parts, respectively, of the reinforcing filler and with the base stabilizer system, consisting of 0 05 parts of ®lrganox 1010 and 0 10 parts of calcium stearate, and also 0 05 parts of the processing stabilizer ©Sandostab P-EPQ or a processing stabilizer combination consisting of 0 04 parts of ©Sandostab P-EPQ and 0 01 parts of a compound of the formula I, in a laboratory mixer, type Melpa 1 (manufacturer Kenwood) Multiple extrusion (passes 1-5) of the mixture takes place in a T4 laboratory extruder, type KPS 25 (manufacturer Haendle) at 270°C or at 300°C through a die having a diameter of 4 millimeters

The following fillers are used specifically

a) talc, type Naintsch SE, b) glass fibers, type R34BX1 (fiber length 4 5 mm), c) carbon fibers, type Sigrafil C (length 6 mm)

The melt index is determined at 230°C using a type 4105 melt index measuring instrument from the manufacturer Zwick and a standard weight of 2 16 kg Tables 1A-D summarize the mfi-results for each 10 parts of filler content considering the fact, that generally for polypropylene a proceeding thermal degradation is reflected by increasing mfi-values.

Tables 2A-D summarize corresponding parameters and results for a filler content of each 20 parts.

Tab.1 A Melt Flow Indices (mfi) of Polypropylene after pre-extrusion at 260°C with and w/o 10 parts filler base stabilization per 100 parts : 0.05% ™lrganox 1010, 0.10 parts Calcium-stearate; 3-arylbenzofuranone according to formula I: R^a = R^c = tert-butyl , R^b, R^d- R^h = H

Tab.1 B Melt Flow Indices (mfi) of Polypropylene after 1^st extrusion pass at 270°C and 300°C with and w/o 10 parts filler; base stabilization per 100 parts : 0.05% ™lrganox 1010, 0.10arts Calcium-stearate; 3-arylbenzofuranone according to formula I: R^a = R^c = tert-butyl , R^b, R^d- R^h = H

Tab.1 C Melt Flow Indices (mfi) of Polypropylene after 3^rd extrusion pass at 270°C and 300°C with and w/o 10 parts filler; base stabilization per 100 parts : 0.05% ™lrganox 1010, 0.10 parts Calcium-stearate; 3-arylbenzofuranone according to formula I: R^a = R^c = tert.-butyl , R^b, R^d- R^h = H

Tab.1 D Melt Flow Indices (mfi) of Polypropylene after 5^th extrusion pass at 270°C and 300°C with and w/o 10 parts filler; base stabilization per 100 parts : 0.05% ™lrganox 1010, 0.10 parts Calcium-stearate; 3-arylbenzofuranone according to formula I: R^a = R^c = tert.-butyl , R^b, R^d- R^h = H

Tab.2 A Melt Flow Indices (mfi) of Polypropylene after pre-extrusion at 260°C with and w/o 10 parts filler base stabilization per 100 parts : 0.05% ™lrganox 1010, 0.10 parts Calcium-stearate; 3-arylbenzofuranone according to formula I: R^a = R^c = tert.-butyl , R^b, R^d- R^h = H

Tab.2 B Melt Flow Indices (mfi) of Polypropylene after 1^st extrusion pass at 270°C and 300°C with and w/o 10 parts filler; base stabilization per 100 parts : 0.05% ™lrganox 1010, 0.10 parts Calcium-stearate; 3-arylbenzofuranone according to formula I: R^a = R^c = tert.-butyl , R^b, R - R^h = H

Tab.2 C Melt Flow Indices (mfi) of Polypropylene after 3^rd extrusion pass at 270°C and 300°C with and w/o 10 parts filler; base stabilization per 100 parts : 0.05% ™lrganox 1010, 0.10 parts Calcium-stearate; 3-arylbenzofuranone according to formula I: R^a = R^c = tert.-butyl , R^b, R^d- R^h = H

Tab.2 D Melt Flow Indices (mfi) of Polypropylene after 5^th extrusion pass at 270°C and 300°C with and w/o 10 parts filler; base stabilization per 100 parts : 0.05% ™lrganox 1010, 0.10 parts Calcium-stearate; 3-arylbenzofuranone according to formula I: R^a = R^c = tert.-butyl , R^b, R^d- R^h = H

EXAMPLE 2

Stabilized low-density polyethylene (PE-LD) is used to produce blown films which are subsequently drawn onto solid substrates by means of a heating press at different temperatures over the course of 5 minutes. The color and surface quality of the laminated PE-LD layer, and its adhesive force to the solid substrate, serve subsequently as measurement parameters. The experiment can be described specifically as follows: 100 parts of polyethylene-LD-powder, type LE 4510 (manufacturer: Borealis) are mixed together with the base stabilizer system, consisting of 0.05 parts of ©Irganox 1076 and 0.05 parts of calcium stearate, and also 0.05 parts of the processing stabilizer ©Sandostab P-EPQ or a processing stabilizer combination consisting of 0.04 parts of ©Sandostab P-EPQ and 0.01 parts of a compound of the formula I, in a laboratory mixer, type Melpa 1 (manufacturer: Kenwood). Extrusion of and production of blown films from the mixture takes place in a T30 laboratory extruder (manufacturer: Collin) at 230°C. This gives films with a thickness of 100 μm. Some of the films are applied to solid substrates by means of a heating press at a temperature of 270°C over a period of 5 minutes. Substrate materials available are paper, board and aluminum. The remainder of the blown films are fixed to the solid substrates by means of a heating press at a temperature of 300°C over the course of 5 minutes, under otherwise identical conditions.

The test parameter measured on the finished device was the tearoff force required for delamination from aluminum plates, in accordance with EN ISO 2409 (cross-cut test).

EN ISO 2409 is one of a series of standards relating to the testing of coatings, binders and similar materials. It specifies a test method for estimating the resistance of a coating to separation from the substrate if a cut going down to the substrate (in this case, the aluminum plate) is scored into the coating. The property measured by this empirical method depends, in addition to other factors, on the adhesion of the coating to the substrate. The method described was practiced in the present case as a classification test with 6 classifications.

The cutting implement had 6 parallel cutting rollers at a distance of 1 mm from each other and was drawn over the coated aluminum plate at room temperature by hand, perpendicularly with respect to the surface of the test plate, and ensuring that the cut went through to the substrate. Subsequently, a cut perpendicular to the first was made in the same way. The cross-cut pattern applied in this way was brushed a number of times back and forward along the diagonals of the pattern using a soft handbrush, and then bonded over with a freshly unrolled, transparent self-adhesive tape, about 7.5 cm long and 25 mm wide, parallel to one direction of the cuts, and was smoothed down using a finger both in the region of the cross-cut pattern and about 20 mm beyond it. Five minutes following the application of the tape, it was removed. This was done by grasping the adhesive tape at one end and tearing it off within about 1 second at an angle of about 60° to the pull direction. Finally, the result was evaluated visually by examination using a magnifying glass providing 2.5χ magnification. For assessment, the plate and the adhesive tape removed from it were examined from different directions.

The test results were classified in accordance with a 6-classification cross-cut scale:

• Cross-cut index 0: the cut edges are completely smoothed, none of the squares of the pattern has flaked off.

• Cross-cut index 1 : small fragments of the coating have flaked off at the intersects of the cross-cut lines. The area of flaking is not substantially greater than 5% of the cross-cut area. • Cross-cut index 2: the coating has flaked along the cut edges and/or at the intersects of the cross-cut lines. The areas of flaking are substantially greater than 5% but not greater than 15% of the cross-cut area.

• Cross-cut index 3: the coating has flaked off along the cut edges, partly or totally in broad strips. A cross-cut area markedly greater than 15% but not substantially greater than 35% is affected.

• Cross-cut index 4: the coating is flaked off along the cut edges in broad strips and/or a number of squares have flaked off completely or partly. A cross-cut area markedly greater than 35% but not substantially greater than 65% is affected.

• Cross-cut index 5: any flaking which cannot be classified using cross-cut index 4.

The samples subjected to this assessment had a polymer film containing on the one hand 0.050% by weight of the commercially available stabilizer Hostanox O 16 and Sandostab P-EPQ (sample A) and a second sample containing the commercial stabilizers Hostanox O 16 (0.050% by weight), Sandostab P-EPQ (0.045% by weight) and a mixture of the compounds 1.1 and 1.2 in a ratio of 9:1 (0.005% by weight) (sample B). As described above, both samples were laminated onto the aluminum support at a temperature of 300°C. The result is set out in the table below:

EXAMPLES for injection molding

Polypropylene samples were produced by injection molding. The products obtained were evaluated by measuring the melt index (MFI) after various dwell times.

Basic stabilization is carried out using ©Irganox 1010 plus calcium stearate and/or zinc stearate. The processing stabilizer used is ©Sandostab P-EPQ alone or in combination with HP 136: mixture of compounds 1.1 and 1.2 as per the above table in a ratio of approximately 9:1; 472: compound 2.8 as per the above table; and

STS 6552/341 : 2'-hydroxy-5'-methyl derivative of compound 2.6 as per the above table. The process can be described specifically as follows:

100 parts of polypropylene powder, type Eltex P HL 001 PF (manufacturer: Solvay Polyolefines) were mixed together with the base stabilizer system and with the processing stabilizer or processing stabilizer combination in a laboratory mixer, type Melpa 1 (manufacturer: Kenwood). Prior extrusion with the mixture took place in a T4 laboratory extruder, type KPS 25 (manufacturer: Haendle) at 220°C / 80 rpm through a die having a diameter of 4 millimeters. Injection molding was carried out in a type T 18 machine (manufacturer: Arburg) at 270°C or 300°C. This involved the polymer melt being injected within a period of 3.2 seconds under a pressure of 90 bar and at an injection rate of 1.2 on a five-point scale through a needle valve nozzle (type: Hertzog M6, diameter 2 mm) into a mold preheated to 60°C. Subsequently, a holding pressure of 50 bar was applied for 3.6 seconds, followed by a cooling interval of 19.5 seconds and then the application of a back pressure of 20 bar. The injection moldings had dimensions of 75 x 50 x 2 mm. The total cycle time was 27.3 seconds. To simulate the conditions in the hot runner, dwell times of 5, 10 and 15 minutes were specified at the respective temperature (270°C or 300°C) before beginning the actual injection molding cycle described above.

The melt index was determined at 230°C using a melt index measuring instrument type 4105 from the manufacturer Zwick and a standard weight of 2.16 kg.

EXAMPLE 3

Extrusion of polypropylene by injection molding at T= 270°C ;

Measurement of the melt index MFI (230°C; 2.16 kg) after a number of dwell times

Base stabilizer system: 0.05% by weight ©Irganox 1010; 0.1% by weight calcium stearate

EXAMPLE 4

Extrusion of polypropylene by injection molding at T= 270°C ;

Measurement of the melt index MFI (230°C; 2.16 kg) after a number of dwell times

Base stabilizer system: 0.05% by weight ©Irganox 1010; 0.1% by weight zinc stearate

EXAMPLE 5

Extrusion of polypropylene by injection molding at T= 300°C ;

Measurement of the melt index MFI (230°C; 2.16 kg) after a number of dwell times

Base stabilizer system: 0.05% by weight ©Irganox 1010; 0.1% by weight calcium stearate

EXAMPLE 6

Extrusion of polypropylene by injection molding at T= 300°C ;

Measurement of the melt index MFI (230°C; 2.16 kg) after a number of dwell times

Base stabilizer system: 0.05% by weight ©Irganox 1010; 0.1% by weight zinc stearate

Claims

What is claimed is:

1. The use of compounds of the formula (I)

in which

R^a, R^b, R^d, R^e, R^f, R⁹ and R^h independently of one another are hydrogen, hydroxyl, d-Ci.alkyl, unsubstituted or mono-, di- or tri-Cι-C alkyl-substituted phenyl, C₇-C₉phenylalkyl, unsubstituted or mono-, di- or tri-d-C alkyl-substituted C₅-C₁₂cycloalkyl or Cι-C₁₈alkoxy and R^c is as defined above for R^a, R^b, R^d, R^β, R^f, R⁹ and R^h or is a radical of the formula (II)

in which

R , R^b, R^d, R^e, R^f, R⁹ and R^h are as defined above and R' and R^J independently of one another are hydrogen or C₁-C₄alkyl, at least two of the radicals R^d, R^e, R^f, R⁹ and R^h being hydrogen, for the stabilization of reinforced thermoplastics, plastic substrates or plastic-coated substrates during their preparation and processing, and of plastics during injection molding by the hot runner technique.

2. The use of compounds as claimed in claim 1 , wherein in formula I R^b is hydrogen and/or

R -R^h are hydrogen and/or

R^a and R^c are C C₁₈alkyl, especially tert-butyl, or unsubstituted or mono-, di- or tri- Cι-C alkyl-substituted phenyl.

The use of compounds as claimed in claim 1 , wherein in formula I R^c is a radical of the formula II and

R' and R¹ are both methyl.

4. The use as claimed in any of claims 1 to 3, wherein the amount of the compound(s) of the formula I in the substrate is from 0.001 to 5% by weight, preferably from 0.002 to 0.05% by weight, based on the polymeric or prepolymeric substrate.

5. The use as claimed in any of claims 1 to 4, wherein the substrate additionally comprises at least one further additive.

6. The use as claimed in claim 5, wherein the substrate comprises as further additive(s) at least one additive selected from the group consisting of organophosphites and/or organophosphonites and/or sterically hindered phenols plus, if desired, sulfur- containing costabilizers and/or sterically hindered amines (HALS) and/or acid scavengers (basic costabilizers).

The use as claimed in claim 5 or 6, wherein each of the further additives is present in a concentration range of from 0.001 to 5% by weight, preferably from 0.01 to 1.0% by weight, based on the polymeric or prepolymeric substrate. A masterbatch composition for stabilizing reinforced thermoplastics during their preparation and processing, comprising at least one compound of the formula I according to claim 1 and a natural or synthetic material identical or compatible with the polymeric or prepolymeric substrate to be stabilized, and, optionally, at least one further additive.

9. A masterbatch composition as claimed in claim 8, wherein the concentration of the compound(s) of the formula I according to claim 1 in the polymeric or prepolymeric substrate to be stabilized is from 1 to 75% by weight, preferably from 2.5 to 30% by weight.

10. A process for stabilizing reinforced thermoplastics during their preparation and processing, for stabilizing plastics substrates or plastic-coated substrates during their production and processing and for stabilizing plastics in the course of injection molding by means of the hot runner technique by adding a stabilizing amount of at least one compound of the formula I according to claim 1 and, if desired, at least one further additive as such or in the form of a masterbatch to the polymeric or prepolymeric substrate to be stabilized.

11. The process as claimed in claim 10, wherein the amount of the compound(s) of the formula I in the substrate is from 0.001 to 5% by weight, preferably from 0.002 to 0.05% by weight, based on the polymeric or prepolymeric substrate.