Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1535—Five-membered rings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques

Definitions

• the present invention relates to the use of compounds of the formula (I)
• R a , R°, R d , R e , R f , R 9 and R h independently of one another are hydrogen, hydroxyl, d-C ⁇ alkyi, unsubstituted or mono-, di- or tri-C ⁇ -C 4 alkyl-substituted phenyl, C 7 -C 9 phenylalkyl, unsubstituted or mono-, di- or tri-C ⁇ -C 4 alkyl-substituted C 5 -C ⁇ 2 cycloalkyl or C Ci ⁇ alkoxy and R c is as defined above for R a , R b , R d , R e , R f , R 9 and R h or is a radical of the formula (II)
• R a , R°, R d , R e , R f , R 9 and R h are as defined above and R' and R 1 independently of one another are hydrogen or C -C 4 alkyl, at least two of the radicals R d , R e , R f , R 9 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.
• R b is hydrogen and/or
• R d -R h are hydrogen and/or
• R a and R c are CrC 18 alkyl, especially tert-butyl, or unsubstituted or mono-, di- or tri- Crdalkyl-substituted phenyl.
• R c is a radical of the above formula II then R' and R' are preferably both methyl.
• 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.
• 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.
• prepregs 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.
• a relatively low viscosity of the thermoplastic polymer often allows these essential requirements to be met.
• it has been found to be disadvantageous that the use of relatively high temperatures is often accompanied by partial decomposition of the matrix polymer.
• 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.
• 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).
• 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.
• 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.
• 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.
• stabilizers or stabilizer combinations 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.
• costabilizers based on metal salts e.g. calcium stearate are added in order to modify the activity of the stabilizers.
• 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%.
• 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.
• 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.
• conventional stabilizers such as organophosphites and organophosphonites, sterically hindered amines and/or, optionally, phenolic antioxidants
• phenolic antioxidants ensure excellent stability of the polymer melt.
• 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.
• 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 remarkably 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.
• 3-phenylbenzofuranones of the formula I according to the invention 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.
• 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 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%.
• 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.
• PP polypropylene
• PE-HD polyethylene
• PE-LD PE-LD
• PE-MD PE-MD
• PE-LLD PE-LLD
• polyamide polyesters
• polyphenylene sulfide polyether ketone
• polycarbonate polyetherimide
• styrene-acrylonitrile polymers polyether sulfone
• polyaryl ether sulfone polyamideimide
• 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.
• 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.
• 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.
• the polymer can also be applied in the form of polymer/wax dispersions, in order finally to form continuous films on the substrate.
• 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.
• 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.
• the layer thicknesses of the polymer phase are in the range between 75 ⁇ m and 500 ⁇ m.
• 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 ⁇ m - 300 ⁇ m) on the substrate; cf. H. Saechtiing, "Kunststoff-Taschenbuch", 26 th Edition (1995); Carl Hanser Verlag, Kunststoff, 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.
• Particularly advantageous monomeric HALS stabilizers are compounds of the formulae A1 to A10.
• R 1 is hydrogen, C 5 -C 7 cycloalkyl or a d-C ⁇ alkyl group and
• R 4 is either hydrogen or a C ⁇ -C 22 alkyl group, an oxygen radical O*, -OH, -NO, CH 2 CN, benzyl, allyl, a d-C 3 oalkoxy group, a C 5 -C 12 cycloalkyloxy group, a C 6 -C ⁇ 0 aryloxy group, where the aryl radical can also be substituted further, a C 7 -C 20 aralkyloxy group, where the aryl radical can also be substituted further, a C 3 -C 10 alkenyl group, a C 3 -C 6 alkynyl group, a d-C 10 acyl group, halogen, or C 7 -C 9 phenylalkyl which is unsubstituted or substituted on the phenyl ring by C 1 -C 4 alkyl, R 6 is an aromatic radical substituted one or more times by hydrogen, C ⁇ -C alkyl, d-C 4 alk
• R and R 4 are as defined above, p is 1 or 2 and
• R 7 is d-C 22 alkyl, C 2 -C 18 oxaalkyl, C 2 -C 18 thiaalkyl, C 2 -C 18 azaalkyl or C 2 -C 8 alkenyl, and
• R 7 is d-d ⁇ alkylene, C -C 8 oxaalkylene, C 2 -C ⁇ 8 thiaalkylene, C 2 -C ⁇ 8 azaalkylene or C 2 -C 8 alkenylene;
• R 1 and R 4 are as defined above,
• R 8 and R 9 independently of one another are hydrogen, d-C 6 alkyl, C 7 -C ⁇ 2 aralkyl, C 7 -C 12 aryl or carboxylate, or R 8 and R 9 together are a tetra- or pentamethyl group;
• R and R 4 are as defined above,
• R 2 and R 3 independently of one another are a hydrogen atom, a d-C 18 alkyl 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)
• R 4 and R 5 independently of one another are either hydrogen or a C C 22 alkyl group, an oxygen radical O*, -OH, -NO, CH 2 CN, benzyl, allyl, a d-C 3 oalkoxy group, a C 5 -C ⁇ 2 cycloalkyloxy group, a C 6 -C 10 aryloxy group, where the aryl radical can also be substituted further, a C 7 -C 2 oarylalkyloxy group, where the aryl radical can also be substituted further, a C 3 -C 10 alkenyl group, a C 3 -C 6 alkynyl group, a d-C 10 acyl group, halogen, or C 7 -C 9 phenylalkyl which is unsubstituted or substituted on the phenyl ring by d-C 4 alkyl, q is 1 or 2,
• R 10 is hydrogen, methyl, phenyl or carb-C 1 -C 2 ⁇ alkoxy
• R 11 is hydrogen or methyl
• R 1 and R 5 are as defined above, and
• R 12 if q 2 is d-C 18 alkylene, C 5 -C 9 cycloalkylene or arylene;
• R 1 , R 4 , R 7 and p are as defined above;
• R 1 , R 4 , R 7 and p are as defined above;
• R 1 and R 4 are as defined above,
• R 30 is hydrogen, d-d 2 alkyl, C 5 -C 12 cycloalkyl, phenyl or C 7 -C 9 phenylalkyl, and a is a number from 1 to 10;
• R 1 and R 4 are as defined above and
• R and R' H , CH 3
• R 1 , R 4 and R 30 are as defined above, and n 5 ', n 5 - and n 5 - independently of one another are a number from 2 to 12.
• R 1 is hydrogen or a C 1 -C alkyl group
• R 2 and R 3 independently of one another are a hydrogen atom, a d-C 8 alkyl 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),
• R 4 and R 5 independently of one another are either hydrogen or a d-C 5 alkyl group, an oxygen radical O * , -OH, -NO, -CH 2 CN, benzyl, allyl, a C C ⁇ 0 alkyloxy group, a C 5 -C 6 cycloalkyloxy group, a C 6 -C 7 aryloxy group, where the aryl radical can also be substituted further; a C 7 -C 10 arylalkyloxy group, where the aryl radical can also be substituted further, a C 3 -C 6 alkenyl group, a C 3 -C 6 alkynyl group, a d-C acyl group, halogen, or C 7 -C 9 phenylalkyl which is unsubstituted or substituted on the phenyl ring by d-C 2 alkyl,
• R 8 and R 9 independently of one another are hydrogen, C 1 -C 2 alkyl, C 7 -C 8 arylalkyl, aryl or carboxylate, j 10 is hydrogen, methyl, phenyl or d-C 2 alkoxy,
• R 1 is hydrogen or methyl
• R 12 if q 2 is d-d 6 alkylene, C 5 -C 6 cycloalkylene or arylene,
• R 30 is hydrogen, C ⁇ -C 8 alkyl, C 5 -C 7 cycloalkyl, phenyl or C 7 -C 8 phenylalkyl, a is from 1 to 5, o is 1 , and p is from 2 to 5.
• R 1 is methyl
• R 2 and R 3 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),
• R 4 and R 5 independently of one another are hydrogen, methyl, acetyl, octyloxy or cyclohexyloxy,
• R 6 is p-methoxyphenyl
• R 8 and R 9 are hydrogen, R 10 is hydrogen,
• R 11 is hydrogen
• R 12 is dodecamethylene or tetradecamethylene
• R 30 is cyclohexyl or n-butyl, a is 2, o is 1 , p is 2, and q is 1.
• 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:
• R 1 is hydrogen, C 5 -C 7 cycloalkyl or a d-C 12 alkyl group
• R 13 is hydrogen or methyl
• R 14 is a direct bond or d-C 10 alkylene, and r is a number from 2 to 50;
• R 15 and R 18 independently of one another are a direct bond or a group
• R 22 and R 24 independently of one another are hydrogen, d-C 8 alkyl, C 5 -C 12 cycloalkyl, phenyl, C 7 -C 9 phenylalkyl or a group of the formula
• R 23 is a direct bond or d-C 4 alkylene
• R 16 , R 17 , R 20 and R 21 independently of one another are hydrogen, d-C 30 alkyl,
• R 9 is hydrogen, d-doalkyl, C 5 -C 12 cycloalkyl, C 7 -C 9 phenylalkyl, phenyl or a group of the formula B2a, and s is a number from 1 to 50;
• R ⁇ R 4 and s are as defined above, and
• R 25 , R 26 , R 27 , R 28 and R 29 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 (CH 2 ) Nh (CH 2 ).
• n 5 ', n 5 - and n 5 - independently of one another are a number from 2 to 12,
• R 30 is as defined above; B4 being a compound of the formula B4-1 , B4-2 or
• n 5 is from 1 to 20
• R 4 and R 30 are as defined above;
• R 31 , R 33 and R 34 independently of one another are hydrogen, d-C 12 alkyl, C 5 -C 12 cycloalkyl, d-C 4 alkyl-substituted C 5 -C 12 cycloalkyl, phenyl, -OH- and/or d-d 0 alkyl- substituted phenyl, C 7 -C 9 phenylalkyl, C 7 -C 9 phenylkalyl substituted on the phenyl radical by -OH and/or d-C ⁇ alkyl, or are a group of the formula B5a
• R 1 and R 5 are as defined above, and
• R 32 is C 2 -C ⁇ 8 alkylene, C 5 -C 7 cycloalkylene or C ⁇ -C 4 alkylenedi(C 5 -C 7 cycloalkylene),
• radicals R 31 , R 32 and R 33 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 R 3 , R 33 and R 34 is a group of the formula B5a;
• R 3i R 32 R 33 and r are as defined above,
• R 35 and R 36 independently of one another can be as defined for R ,3 J 4 4 , or R 35 and R 36 , 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 R 31 , R 33 , R 35 and/or R 36 is a group of the formula (B5a);
• R 1 and R 4 are as defined above, s is as defined for formula B3,
• R 37 is d-C 10 alkyl, C 5 -C 12 cycloalkyl, d-C 4 alkyl-substituted C 5 -C 12 cycloalkyl, phenyl or
• 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.
• an organic solvent such as 1 ,2-dichloroethane, toluene, xylene, benzene, dioxane or tert-amyl alcohol
• 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.
• 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.
• 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.
• R 1 is hydrogen or a C C 4 alkyl group
• R 2 and R 3 independently of one another are a hydrogen atom, a d-C 8 alkyl 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),
• R 4 and R 5 independently of one another are either hydrogen or a d-C 5 alkyl group, an oxygen radical O*, -OH, -NO, -CH 2 CN, benzyl, allyl, a d-Cioalkyloxy group, a C 5 -C 6 cycloalkyloxy group, a C 6 -C 7 aryloxy group, where the aryl radical can also be substituted further, a C 7 -C 10 arylalkyloxy group, where the aryl radical can also be substituted further, a C 3 -C 6 alkenyl group, a C 3 -C 6 alkynyl group, a d-C 4 acyl group, halogen, or C 7 -C 9 phenylalkyl which is unsubstituted or substituted on the phenyl ring by d-C 2 alkyl,
• R 13 is hydrogen or methyl
• R 14 is d-C 5 alkylene
• R 7 and R 2 are hydrogen or d-C 4 alkyl
• R 15 and R 18 are a direct bond
• R 6 and R 20 are d-C 25 aikyl or phenyl
• R 19 is hydrogen, d-C 12 alkyl or a group of the formula B2a,
• R 25 , R 26 , R 27 , R 28 and R 29 independently of one another are a direct bond or d-C 5 alkylene
• R 30 is hydrogen, C ⁇ -C alkyl, C 5 -C 6 cycloalkyl or phenyl,
• R 31 , R 33 and R 34 independently of one another are hydrogen, d-C 10 alkyl,
• R 32 is C 2 -C 10 alkylene or C 5 -C 6 cycloalkylene
• R 35 and R 36 independently of one another are as defined for R 34 , or R 35 and
• R 36 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 R 31 , R 33 , R 35 and/or R 36 is a group of the formula B5a,
• R 37 is d-C 5 alkyl, C 5 -C 6 cycloalkyl or phenyl,
• R 38 C 3 -C 5 alkylene, and n 5' ,n 5 ',n 5 - are from 2 to 4.
• R 4 and R 5 independently of one another are hydrogen, acetyl, methyl, octyloxy or cyclohexyloxy,
• R 3 is hydrogen
• R 14 is ethylene
• R 17 and R 21 are hydrogen or methyl
• R 15 and R 8 are a direct bond
• R 16 and R 20 are d-C 25 alkyl or phenyl
• R 19 is hexadecyl or a group of the formula B2a,
• R 25 and R 27 are methylene
• R 26 is a direct bond
• R 28 is 2,2-dimethylethylene
• R 29 is 1 ,1-dimethylethylene
• R 30 is n-butyl
• R 31 , R 33 and R 34 independently of one another are isooctyl, cyclohexyi or 2,2,6,6- tetramethylpiperid-4-yl, at least one of the radicals R 31 , R 33 and R 34 having to be 2,2,6, 6-tetramethylpiperid-4-yl,
• R 32 is hexamethylene
• R 35 and R 36 independently of one another are as defined for R 34 , or R 35 and R 36 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 R 31 , R 33 , R 35 and/or R 36 having to be a 2,2,6,6-tetramethylpiperid-4-yl radical,
• R 37 is methyl
• R 38 is trimethylene, n 5 ',n 5 ",n 5" are from 2 to 4.
• polymeric HALS compounds comprise the following substances:
• B'10 is a compound of the formula B4-1', B4-2' or B4-3'
• n 5 is from 1 to 20.
• ® 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.
• 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:
• 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
• A' if n' is 3, is a radical of the formula -C r H 2r - ⁇ ;
• A' if n' is 4, is the radical of the formula C(CH 2 ) 4 -;
• A" is as defined for A' if n' is 2;
• B' is a radical of the formula -CH 2 -; -CHR' 4 -; -CR' T R ; -S- or a direct bond; or is
• C 5 -C 7 cycloalkylidene or is cyclohexylidene substituted by from 1 to 4 C 1 -C 4 alkyl radicals in positions 3, 4 and/or 5, D', if u is 1 , is methyl and, if u is 2, is -CH 2 OCH 2 -;
• E' if y is 1 , is alkyl having 1 to 18 carbon atoms, phenyl, a radical of the formula -OR 1 ! 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' 4 C(CH 2 O) 3 - or N(CH 2 -CH 2 -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' ⁇ , R' 2 and R' 3 independently of one another are alkyl having 1 to 30 carbon atoms; halogen-, -COORV, -CN- or -CONR' 4 R' 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-C 1 -C 4 alkyi; or a radical of the formula
• 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' 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; -CH 2 -; -C(R' ⁇ 6 ) 2 - or -S-.
• n' is 2 and y is 1 or 2;
• R' L R' 2 and R' 3 independently of one another are alkyl having 1 to 18 carbon atoms; phenyl-d-C 4 alkyl; 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-
• 71 is a direct bond or -CH(R' 16 )-.
• n' is 2 and y is 1;
• A' is p-biphenylene
• E' is d-Ci ⁇ alkoxy
• R' ⁇ , 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-
• Z' is a direct bond, -CH 2 - or -CH(CH 3 )-.
• 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.
• light stabilizers such as those, for example, from the class of the UV absorbers (2-hydroxybenzophenones or 2-hydroxyphenylbenzotriazoles, cinnamic acid derivatives, oxaniiides
• nickel quenchers in a synergistic manner.
• 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.
• 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 half, ® 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.
• 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.
• 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).
• HDPE high density polyethylene
• HDPE-HMW polyethylene of high density and high molar mass
• HDPE-UHMW polyethylene of high density and ultrahigh molar mass
• HMDPE medium density polyethylene
• LDPE low
• 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 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 ⁇ - or ⁇ -coordinated.
• ligands such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -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).
• 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)
• Hydrocarbon resins for example C 5 -C 9
• hydrogenated modifications thereof e.g. tackifier resins
• mixtures of polyalkylenes and starch
• Polystyrene poly(p-methylstyrene), poly( ⁇ -methylstyrene).
• Copolymers of styrene or ⁇ -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/but
• Graft copolymers of styrene or ⁇ -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
• 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.
• halogen-containing polymers such as polychloroprene, chlorinated rubber, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or
• 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.
• acrylonitrile-butadiene copolymers for example acrylonitrile-butadiene copolymers, acrylonithlealkyl acrylate copolymers, acrylonitrilealkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrilealkyl methacrylate-butadiene terpolymers.
• cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisgiycidyl ethers.
• Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain comonomers, for example ethylene oxide; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
• 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.
• polyethers e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol.
• polyamides or copolyamides modified with EPDM or ABS and polyamides condensed during processing (RIM polyamide systems).
• Polyureas Polyureas, polyimides, polyamide-imides, polyether imides, polyester amides, polyhydantoins and polybenzimidazoles.
• 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.
• 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.
• Crosslinkable acrylic resins derived from substituted acrylates for example from epoxy acrylates, urethane acrylates or polyester acrylates.
• alkyd resins 25. alkyd resins, polyester resins and acrylic resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
• 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.
• 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.
• 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.
• 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.
• synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
• 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:
• 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-( ⁇ -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-d
• alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4- dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6- didodecylthiomethyl-4-nonylphenol.
• alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4- dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6- didodecylthiomethyl-4-nonylphenol.
• 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.
• 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.
• 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-d
• 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-( ⁇ - 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-( ⁇ -methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ - dimethylbenzyl)-4-nonyl
• 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.
• 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.
• dioctadecyl 2,2-bis(3,5-di-tert-butyl-2- hydroxybenzyl)malonate dioctadecyl 2-(3-tert-butyl-4-hydroxy-5- methylbenzyl)malonate
• 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.
• 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,
• 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.
• esters of ⁇ -(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
• esters of ⁇ -(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-trio
• esters of ⁇ -(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-
• 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-trioxabicycl
• 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
• 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'
• 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
• 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
• 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.
• 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.
• 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
• 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-octylamin
• 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.
• 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.
• 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, bisis
• 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.
• 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-dia
• (M 2+ ) is Mg, Ca, Sr, Ba, Zn, Pb, Sn, Ni
• a n 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 “ , CIO 4 -, CH 3 COO ⁇ C 6 H 5 COO-, CO 3 2" , SO 4 2 ⁇ (OOC-COO) 2 -, (CHOHCOO) 2 2' , (CHOH) 4 CH 2 OHCOO " , C 2 H 4 (COO) 2 2” , (CH 2 COO) 2 2' , CH 3 CHOHCOO " , SiO 3 2" , SiO 4 4' , Fe(CN) 6 3” , Fe(CN) 6 4 -, BO 3 3” , PO 3 3” , HPO 4 2" .
• hydrotalcites in which (M 2+ ) is (Ca 2+ ), (Mg 2+ ) or a mixture of (Mg 2+ ) and (Zn 2+ ); (A n" ) is CO 3 2' , BO 3 3" , PO 3 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
• (M 2+ ) is Mg 2+ , Zn 2+ , but more preferably Mg 2+ .
• (A n" ) is an anion, in particular from the group consisting of CO 3 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:
• 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.
• Peroxide scavengers examples being esters of ⁇ -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( ⁇ - dodecylmercapto)propionate.
• esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl ester, mecaptobenzimidazole, the zinc salt of 2- mercaptobenzimidazole, zinc alkyldithiocarbama.es, zinc dibutyldi
• Polyamide stabilizers examples being copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
• 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.
• 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.
• metal oxides such as titanium oxide or magnesium oxide
• 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.
• 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.
• talc talc
• type Naintsch SE 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.
• PE-LD Stabilized low-density polyethylene
• 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.
• films with a thickness of 100 ⁇ m 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.
• test results were classified in accordance with a 6-classification cross-cut scale:
• 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.
• 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).
• both samples were laminated onto the aluminum support at a temperature of 300°C. The result is set out in the table below:
• Polypropylene samples were produced by injection molding. The products obtained were evaluated by measuring the melt index (MFI) after various dwell times.
• MFI melt index
• 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
• 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.
• Base stabilizer system 0.05% by weight ⁇ Irganox 1010; 0.1% by weight calcium stearate
• Base stabilizer system 0.05% by weight ⁇ Irganox 1010; 0.1% by weight zinc stearate
• Base stabilizer system 0.05% by weight ⁇ Irganox 1010; 0.1% by weight calcium stearate
• Base stabilizer system 0.05% by weight ⁇ Irganox 1010; 0.1% by weight zinc stearate

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