MXPA06008280A - Method of producing low-dust granules from polymer additives - Google Patents

Abstract

The invention relates to a technically advantageous method of producing low-dust granules of polymer additives or polymer additive mixtures. The granule-forming polymer additives are mixed together, the mixture is converted into a workable mass and pressed through an orifice. The pre-shaped strand-like extruded mass is cooled and, while still in a workable state, formed into granules by rolling, impressing, cooling and comminuting.

Description

METHOD FOR PRODUCING GRANULES WITH LOW CONTENT OF POLYMER ADDITIVE POWDER FIELD OF THE INVENTION The present invention relates to a method for producing low dust granules of polymer additives.

BACKGROUND OF THE INVENTION Organic polymers, especially polyolefins, generally require the addition of additives in order to facilitate processing and retain the properties in use for as long a period as possible. Factors that have a damaging effect on organic polymers, in addition to light and heat, also include residues of catalysts used during the preparation. The prior art describes a large number of classes of substances that can be used as additives and stabilizers. Because of the complex processes (not all of which have been explained in detail) that result in the degradation of the organic polymers, mixtures of a plurality of additives are often used. In general, the additives and admixtures of additives are in the form of powder, which can be disadvantageous, examples of the disadvantages including the formation of dust, the tendency to separate and problems of dosing. Therefore, there is a need for commercial product forms that are not associated with those disadvantages. Examples of known methods include agglomeration methods, for example, in aqueous phase, optionally with the use of a dispersant, methods of mixing with binders, and compaction using a granulation press. In many cases, the resulting forms of commercial products have defects. They often contain water or binders, which are disadvantageous for incorporation into organic polymers. Accordingly, there is a need for mixtures of granular additives having good properties in use that comprise little or no binder. In addition, mixtures of granular additives need to satisfy increasingly the relevant ecological criteria, for example, little dust formation, material savings through the omission of the binder, etc. US Patent Specification No. 5,240,642 discloses a method for producing granular forms of additives to neutralize organic and inorganic acids and tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionyloxymethyl] methane. This method is carried out in the presence of the aforementioned material in the molten state, that material that is distributed homogeneously throughout the entire powdery mass of the acid neutralizing agent, the mass that is extruded, the extruded strands that they cool and then the granules are formed. The granules that can be obtained in this manner have disadvantages, however, since they cause substantial amounts of dust. European Patent Application No. 719,824 discloses a method for producing low-dust calcium stearate granules, more specifically by heating calcium stearate or a mixture of additives comprising calcium stearate and additional polymer additives, extruding through of a plate provided with nozzles or holes, the diameter of the nozzles or holes that is from 1.0 to 10.0 mm, and subsequently forming the granules directly from the resulting extruded product while still in a plastic state (called "cut in"). hot" ) . This method also has disadvantages, because for the extrusion, the viscosity of the mass of the product must be adjusted to a low value, by supplying or removing heat, such that the mass of the product remains plastic in the passage through the holes. This is especially critical in the case of mixtures of additives, which have a tendency to harden. On the other hand, a high viscosity is required to cut the strands of the product during the formation of the granules in order to prevent the mass of the product from adhering to the cutting device. Therefore, there is a need for an improved method that allows granules to be formed in a subsequent step, separately from extrusion.

Description of the Invention The present invention is based on a method in which a small number of holes is required or only one hole is required, for the extrusion and the granules are formed in a subsequent step. The principle of the method according to the invention is to provide the extruder with only a small number of holes, prefey with only one hole (hole or slot). The pre-formed, emergent plastic mass is then laminated to the required granule thickness using a pair of rollers (calenders), deposited in a cooling band and transported additionally. In the next step, the size of the granule is fixed on the resulting paste mat using forming rollers. The lower part of the band is cooled in order to harden the plastic mass. At the end of the band, the hardened, fixed paste mat is subjected to preliminary disintegration into coarse pieces which are then broken into individual granules in a sieve granulator. The invention relates to a technically advantageous method for producing low-powder granules of polymer additives or mixtures of polymer additives (mixtures), where the granular-forming polymer additives are mixed together, the mixture becomes a workable mass and pressed or pressed through a hole, and the pre-formed extruded, strand-like mass is cooled and while still in a workable state, is formed into granules by rolling, fixing, cooling and grinding. The granules that can be produced according to this method are formed uniformly and are distinguished by excellent technical properties with respect to their further processing, especially advantageous properties of bulk material, for example, particle size adjustable from 1.0 to 10.0 mm Bulk bulk density of more than 400 g / 1, good fluidity, for example, spill speeds of 2 to 40 seconds (according to DIN 53492 by measurement of tR? 5 and tR2s, measurement of spill velocity using a funnel having a defined outlet opening, for example 15 and 25 mm), resting angles of the poured material of 30-40 ° in accordance with ISO 4324 (DIN ISO 4324), considee resistance to wear and freedom of dust, example, very low dust levels in the Heubach test, and also good stability in operation. Therefore, orifices that are to be stabilized can be easily dosed into the polymer polymers. In the production of granules, a low dust content is an important criterion, which is determined according to the so-called Heubach test in an experimental setup that is similar to conditions in practice, the test material being kept in motion at In order to determine the tendency to dust formation based on dust emissions caused by wear. The test apparatus is manufactured by Heubach Engineering, Langelsheim (DE). In the test, the test material (50 g sample weight) moves at 30 rpm (revolutions per minute), which corresponds to a circumferential speed of approximately 19 centimeters / second, for 5 minutes in a powder production system which has a capacity of 2.5 liters, where three deflectors are arranged in the direction of rotation at an angle of 45 ° to the wall of the housing, while an air flow of 0.32 liters / seconds deposits the fine components in a filter . The content of fine particles determined in this way does not preferentially exceed the value of 0.1% by weight. In a preferred embodiment of the invention, the phenolic polymer additives of the formula are mixed together as granule-forming polymer additives: wherein, independently of each other, one of Ri and R2 is hydrogen, a substituent selected from the group Cx-Cj.8alkyl, phenyl, (Cx-C alkyl) X-3-enyl, f-C-C3-alkyl, (C? -C4alkyl)? -3-phenyl-C? -C3alkyl, C5-C? 2-cycloalkyl and. { C? ~ C alkyl)? 3 C5-C12 cycloalkyl or a group of the formula: wherein Ra is hydrogen or a substituent selected from the group C? -C4alkyl, halogen and sulfo; and the other is a substituent selected from the group C? -C18alkyl, phenyl, (C? -C4alkyl)? -3phenyl, phenyl-Ci-C3alkyl, (C? -C4alkyl)? _3phenyl-Ca-C3alkyl, C5-C? 2-cycloalkyl and (C? -C4alkyl) 1_3C5-C? 2-cycloalkyl or a group of the partial formula (A), wherein Ra is as defined; R3 is hydrogen or methyl; m is a number zero or 1; and n is an integer from 1 to 4; where, when n is the number 1, m is zero or 1 and Y denotes a monovalent substituent -0-Y? or -N (-Y) 2, wherein Yx is C5-C45alkyl, C3.C45alkyl interrupted by at least one oxygen atom, C5-C12cycloalkyl, C-C2alkenyl, a substituent of the partial formula -CH2-CH ( OH) -CH2-0-C (= 0) -Rb, (B), wherein Rb is hydrogen, Cx-C-alkyl, C3-C5alkenyl or benzyl, a substituent of the partial formula -CH2-CH2-0-Rc ( C), wherein Rc is hydrogen, C-C24alkyl, C5-C12cycloalkyl or phenyl, a substituent of the partial formula -CH2-CH2-0-CHRd-CHRc-C (= 0) -0-Rf (D), in where one of Rd and Re is hydrogen or methyl and the other is methyl, and Rf is hydrogen or C? -C24alkyl, a substituent of the partial formula wherein i and R2 are as defined above, or a substituent of the partial formula -CH2-CH2-0-CH2-C (= 0) -O-Rg (F), wherein Rg is hydrogen or C, -C24alkyl; and Y2 is hydroxy-C2-C4alkyl; or, when n is the number 2, m is zero and Y is a bivalent group of the partial formula -0-CxH2x-0- (G), where x is an integer from 2 to 20, -O- (CH2- CH2-0) y-CH2-CH2-0- (H), where y is an integer from 1 to 30, -0-CH2-CH2-S-CH2-CH2-0- (I), -0- CH2-CH = CH-CH2-0- (K) or -NH- (CH2) 2-NH- (L), where z is zero or an integer from two to ten; or when n is the number 3, m is zero and Y is a trivalent group of the partial formula wherein Rh is C? -C2 alkyl or phenyl, or when n is the number 4, m is zero and Y is the tetravalent group of the partial formula Alkyl groups of various chain lengths defined in the description of the present invention include linear hydrocarbon radicals and where possible branched, especially C? -C9alkyl, eg, methyl, ethyl, isopropyl, n-butyl, isobutyl, ter- butyl, n-pentyl, neopentyl, isopentyl, n-hexyl, 2-ethylbutyl, 1-methylpentyl, 1,3-dimethylbutyl, n-heptyl, 3-heptyl, 1-methylhexyl, isoheptyl, n-octyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, n-nonyl or 1,1,3-trimethylhexyl, also C? 0-C45alkyl, especially C10-C5 straight-chain alkyl, for example, n-decyl, n- dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, icosyl, henicosyl, docosyl or triacontyl, or C10-C22alkyl branched, eg, 1,3-trimethylhexyl, 1-methylundecyl, 2-n-butyl-n -octyl, iso-tridecyl, 2-n-hexyl-n-decyl or 2-n-octyl-n-dodecyl, or higher homologs thereof. (C? -Calkyl)? -3-phenyl is for example 2- or 4-tolyl, 2,5- or 2,6-xylyl, mesityl, 2- or 4-ethylphenyl, 2,4- or 2,6-diethylphenyl, -quartil, 2-tert-butyl-6-methylphenyl or 2,6-bis-tert-butyl. Phenyl-C? -C3alkyl is for example phenyl linked to C? -C3alkyl in the 1, 2 or 3 position, for example, 2-phenylethyl, especially benzyl. (C? -C4alkyl)? -3-phenyl-C? -C3alkyl is one of the (C? -C4alkyl)? .3-phenyl radicals defined above attached to C? -C3alkyl in the 1, 2 or 3 position, for example 2-ter -butyl-6-methylbenzyl or 2,6-bis-tert-butylphenyl. C 5 -C 12 cycloalkyl is for example cyclopentyl or cyclohexyl. (C? -C4alkyl)? -3C5-C12cycloalkyl is one of the C5-C1-cycloalkyl groups defined above substituted by 1-3C? -C4alkyl, for example, 2- or 4-methylcyclohexyl, 2, 6-dimethylcyclohexyl, 2,4,6-trimethyl-cyclohexyl or 4-tert-butylcyclohexyl. Alkenyl is for example vinyl, allyl, 2-butenyl, methallyl, 2- or 3-hexenyl, or 3- or 5-decenyl. In addition, the partial formula (A) defined above includes the following positional isomer: Ra as halogen is bromine, iodine or especially chlorine. In a compound (I), the subscript m is zero or one.

When m is zero, this defines the direct link. According to a further embodiment, the subscripts m and n are the number 1. And in this case, the monovalent group -0-Yx. These compounds (I) correspond to the formula: Yx as C3-C45alkyl interrupted by at least one -O-heteroatom includes the C3-C5alkyl groups mentioned above, especially 2-methoxyethyl, 2- or 3-methoxypropyl, 2-, 3- or 4-methoxy-butyl, 2-ethoxyethyl , 2- or 3-ethoxypropyl, 2-, 3- or 4-ethoxybutyl, 2-n-propoxyethyl, 2-or 3-n-propoxypropyl, 2-, 3- or 4-n-propoxybutyl, 2-isopropoxyethyl, 2 - or 3-isopropoxypropyl, 2-, 3- or 4-isopropoxybutyl, 2-n-butoxyethyl, 2- or 3-n-butoxypropyl, 2-, 3- or 4-n-butoxybutyl, 2-tert-butoxyethyl, 2 or 3-tert-butoxypropyl, 2-, 3- or 4-tert-butoxybutyl and higher homologs thereof, especially C5-C? 8 linear alkyl substituted by methoxy, ethoxy, n-propoxy, isopropoxy or by tert-butoxy. Rb in a group of the partial formula (A) is preferably hydrogen, allyl, methallyl or benzyl. Rc in a group of the partial formula (C) is preferably hydrogen or C? -Calkyl.

Y 2 as hydroxy-C-Calkyl is preferably 2-hydroxyethyl. An especially preferred group of compounds (I), where m is zero and defines the direct link and n is one, corresponds to the following general formulas: In these compounds, one of R and R2 is methyl or tert-butyl and the other of Rx and R2 is tert-butyl, Yx is C10-C22 straight or branched chain alkyl and Y2 is 2-hydroxyethyl. An especially preferred additional group of compounds (I), wherein 'm is zero and defines the direct bond and n is one, corresponds to the general formula: wherein Ra is hydrogen or chloro and Y is C10-C22 straight or branched chain alkyl. According to a preferred additional embodiment, the polymer additives (I), phenolics where n is number 2 and m are zero are mixed together as granule-forming polymer additives. Y denotes a bivalent substituent selected from the group -0-CxH2x-0- (G), where x is an integer from 2 to 20, -O- (CH2-CH2-0) and -CH2-CH2-0- ( H), where y is an integer from 1 to 30, -0-CH2-CH2-S-CH2-CH2-0- (I), -0-CH2-CH = CH-CH2-0 - (K); and -NH- (CH2) Z-NH- (L), wherein z is zero or an integer from 2 to 10. Preferred compounds correspond to the formulas wherein Ra is hydrogen or tert-butyl. A further preferred embodiment refers to the preparation of the compounds (I) wherein n is the number 3, m is zero and Y is the trivalent group This compound corresponds to the formula A further preferred embodiment refers to the preparation of the compounds (I) wherein n is the number 4 and m is zero. This compound corresponds to the formula In a further preferred embodiment of the invention, polymer additives (I), phenolic additives are mixed together as granule-forming polymer additives, wherein one of Rx and R2 is methyl, tert-butyl or the group (A) wherein Ra is hydrogen or chlorine, and the other of R and R2 is tert-butyl; R3 is hydrogen; m is zero or the number 1; and n is an integer from 1 to 4; where, when n is number 1, m is zero or number 1 and Y corresponds to the monovalent group -0-Y? or -N (-Y2) or n is the number 2, m is zero and Y denotes a bivalent group of the partial formula (D), (E), (F), (G) or (H); or n is the number 3, m is zero and Y denotes a trivalent group of the partial formula (K) or (L); or n is the number 4 and m is zero and Y denotes a tetravalent group of the partial formula (M). According to an especially preferred embodiment, the polymer phenolic additives of the formula are mixed together as granule-forming polymer additives: wherein, independently of one another, one of R and R2 is hydrogen or C-C4alkyl and the other is C3-C4alkyl; x is zero (direct link) or an integer from one to three; and Y is C8-C2alkoxy or a group of the partial formula wherein, independently of each other, one of Rx 'and R2' is hydrogen or C? -C4alkyl and the other is C3-C4alkyl; x is zero (direct link) or an integer from one to three; and is an integer from two to ten and z is an integer from two to six. The following additional polymer additives can be mixed together with the polymer, phenolic, granule-forming additives described above to form the so-called mixtures: 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-iso-butylphenol, 2,6-dicyclopentyl-4- methylphenol, 2- (a, a-methylcyclohexyl) -4, 6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, straight or branched chain nonylphenols; for example, 2, 6-dinoyl-4-methylphenol, 2,4-dimethyl-6- (1-methylundec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyl-heptadec- 1 '-yl) -phenol, 2,4-dimethyl-6- (1'-methyltride-1-yl) -phenol and mixtures thereof. 1.2 Alkyltiomethylphenols, 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 Tocopherols, for example, -, ß-,? - or d-tocopherols and mixtures thereof (vitamin E). 1.5 Hydroxylated thiodiphenyl ethers, for example, 2,2'-thio-bis (6-tert-butyl-4-methylphenol), 2,2'-thio-bis (4-octylphenol), 4,4'-thio- bis (6-tert-butyl-3-methylphenol), 4,4'-thio-bis (6-tert-butyl-2-methylphenol), 4,4'-thio-bis (3,6-di-sec- amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxy-phenyl) -disulfide. 1. 6 Alkylidene-bis-phenols, for example, 2,2'-methylene-bis (6-tert-butyl-4-methylphenol), 2,2'-methylene-bis (6-tert-butyl-4-ethylphenol), 2,2'-methylene-bis [4-methyl-6- (a-methylcyclohexyl) -phenol], 2,2'-methylene-bis (4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis (6-nonyl-4-methylphenol), 2,2'-methylene-bis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis [6- (a-methylbenzyl) -4-nonylphenol], 2,2'-methylene-bis [6- (a, a-dimethylbenzyl) -4-nonylphenol], 4,4'-methylene-bis (2,6-di-tert-butylphenol), 4,4'-methylene-bis (6-ter) -butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1, 1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) - 3-n-dodecylmercapto-butane, ethylene glycol bis [3, 3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-) methylphenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl) -2-hydroxy-phenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) ) -4-n-dodecyl mercaptobutane, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane. 1.7 Compound of 0-, N- and S-benzyl, for example, 3, 5, 3 ', 5' -tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3, 5 -dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl) -hydroxy-2,6-dimethylbenzyl) -dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) -sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetate. 1.8 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. 1.9 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. 1.10 Triazine 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-hydroxy-benzyl) -isocyanurate. 1.11 Benzyl phosphonates, for example, dimethyl-2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, dioctadecyl-3, 5- di-tert-butyl-4-hydroxybenzyl phosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzyl phosphonate, calcium salt of the 3,5-di-tert-butyl-4- monoethyl ester hydroxybenzylphosphonic 1.12 Acylaminophenols, for example, 4-hydroxylauranylide, 4-hydroxysteatenylidene, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbamate. 1.13 Ascorbic acid (vitamin C). 1.14 Amine antioxidants, for example, N, N'-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethyl-pentyl) -p phenylenediamine, N, N'-bis (l-ethyl-3-methyl-pentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p- phenylenediamine, N, N '-diphenyl-p-phenylenediamine, N, N' -di (2-naphthyl) -p-phenylenediamine, N-isopropyl-N '-phenyl-p-phenylenediamine, N- (1,3-dimethyl) -butyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N '-phenyl-p-phenylenediamine, 4- (p-toluenesulfonamido) -diphenylamine, N, H-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenyl-amine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-ter) octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example, 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-diphenylaminopropane, o-tolylbiguanide, di [4- (1,3'-dimethylbutyl) phenyl] amine, N-phenyl-1-naphthylamine tert-octylated , a mixture of mono- and di-alkylated tert-butyl- / tert-octyl-diphenylamines, a mixture of mono- and di-alkylated nonildiphenylamines, a mixture of mono- and di-alkylated dodecyldiphenylamines, a mixture of isopropyl- / isohexyl mono- and di-alkylated diphenylamines, mixtures of mono- and di-alkylated tert-butyldiphenylamines, 2,3-dihydro-3, 3-dimethyl-4H-1, 4-benzothiazines, phenothiazines, a mixture of tert-butyl- / mono- and di-alkylated tert-octyl-phenothiazines, a mixture of mono- and di-alkylated tert-octyl-phenothiazines, N-allylphenothiazines, N, N, N ', N'-tetraphenyl-1,4-diaminobutyl- 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 and 2, 2, 6,6-tetramethylpiperidin-4-ol. 1.15 Polyphenolic antioxidants, for example, derivatives of p-cresol and dicyclopentadiene, for example, ® WINGSTAY L (Goodyear), CAS-No. 68610-51 -5. 2. UV Absorbers and Light Stabilizers 2.1 2 (2'-Hydroxyphenebenzotriazoles, 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 '-seg -butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3', 5'-di- ter-amyl-2 '-hydroxyphenyl) benzotriazole, 2- (3', 5'-bis (a, -dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy) 5 '- (2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, - (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-octyloxycarbonylethyl) phenyl ) benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-51-methylphenyl) ) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) -phenylbenzotriazole, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl ) -6-benzotriazol-2-yl-phenol]; the transesterification product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylenegluol 300; wherein R is 3 '-tert-butyl-4' -hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2 - [2'-hydroxy-3 '- (a, a-di-ethylbenzyl) -5' - (1,1,3,3-tetramethylbutyl) fenilibenzotriazole; 2- [2'-Hydroxy-3 '- (1, 1,3,3-tetramethylbutyl) -5' - (a, a-dimethylbenzylbenzyl) phenyl] benzotriazole. 2.2 2 -Hydroxybenzophenones, for example, 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4, 2 ', 4'-trihydroxy or 2'-hydroxy-4 derivatives , 4'-dimethoxy. 2.3 Esters of benzoic acid, 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-α-cyano-β, β-diphenylacrylate or isooctyl-α-cyano-β, β-diphenylacrylate, methyl-α-carbomethoxycinnamate, methyl-α-cyano-β-methyl-p-methoxycinnamate or butyl-α-cyano-β-methyl-p-methoxycinnamate, methyl-α-carbomethoxy-p-methoxycinnamate and N- (α-carbomethoxy-β-cyanovinyl) -2-methylindoline. 2.5 Nickel compounds, for example, 2, 2'-thio-bis [4- (1, 1,3, 3-tetramethylbutyl) -phenol] nickel complexes, for example, the 1: 1 or 1: 2 complex , optionally with additional ligands, for example, n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, for example, methyl or ethyl esters, 4-hydroxy-3, 5-di -tert-butylbenzylphosphonic, nickel complexes of ketoximins, for example, 2-hydroxy-4-methylphenylundecyl-ketoximes or nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with additional ligands. 2.6 The so-called sterically hindered amines, for example, bis (2, 2, 6, 6-tetramethylpiperidin-4-yl) -sebacate, is (2,2,6,6-tetramethylpiperidin-4-yl) -succinate, is ( 1, 2, 2, 6, 6-pentamethylpiperidin-4-yl) -sebacate, bis (l-octyloxy-2, 2,6,6-tetramethylpiperidin-4-yl) -sebacate, bis (1, 2, 2, 6,6-pentamethylpiperidin) -n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate, the condensate of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid , the linear or cyclic condensate of N, N '-bis (2, 2, 6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2, 6-dichloro-1, 3, 5-s-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) itrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) - 1,2,3,4-butanetetraate, 1,1'- (1,2-ethanediyl) -bis (3, 3, 5, 5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,6,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-ter- butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-l, 3,8-triazaspiro [4.5] decane-2,4-dione, bis (l-octyloxy-2, 2, 6, 6-tetramethylpiperidyl) sebacate, bis (l-octyloxy-2, 2,6,6-tetramethylpiperidyl) succinate, the linear or cyclic condensates 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 2-chloro-4,6-di (4-n-butylamino-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-n-butylamino-1,2, 2,6,6- pentamethylpiperidyl) -1,3,5-triazine and 1, 2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7, 7,9, 9-tetramethyl-l, 3,8-triazaspiro- [4,5] decane-2,4-dione, 3-dodecyl -l- (2, 2, 6, 6-tetramethyl-4-piperidyl) pyrrolidine-2, 5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine -2, 5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2, 2, 6, 6-tetramethylpiperidine, the condensate of N, N'bis (2, 2, 6, 6-tetramethyl-4 - piperidyl) -hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, the condensate of 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3, 5-triazine and 4-butylamino-2, 2, 6, 6-tetramethylpiperidine (CAS No. 136504-96-6); ? - (2, 2, 6, 6-tetramethyl-4-piperidyl) -n-dodecyl succinimide,? - (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) -n-dodecyl succinimide, 2-undecyl- 7, 7,9, 9-tetramethyl-l-oxa-3,8-diaza-4-oxospiro [4.5] decane, the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-oxa -3, 8-diaza-4-oxospiro [4.5] decane and epichlorohydrin, 1, 1-bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) -ether, ?,? ' -bis-formil -?,? ' -bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, the diester of 4-methoxymethylenemalonic acid, with 1, 2, 2, 6, 6-pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-] oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, the reaction product of maleic anhydride / α-olefin copolymer and 2,2,6,6-tetramethyl-4-aminopiperidine or 1, 2, 2, 6, 6-pentamethyl-4-aminopiperidine. 2.7 Oxalamides, for example, 4,4'-dioctyloxyoxanilide, 2,2 '-dietoxyoxanilide, 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 the mixture with 2-ethoxy- '-ethyl-5,4' -di-tert-butyloxanilide and mixtures of o- and p-methoxy- and 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, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4) -octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-di-methylphenyl) - 1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4-] (2-hydroxy-3-butoxypropyloxy) 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- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6- bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxy-propoxy) phenyl] -4,6-bis (2, 4- dimetilfe nil) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) - 4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxy-propoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2-. { 2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine. 3. Metal deactivators, for example, N, N'-diphenyloxalamide, N-salicylal-N '-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-ter- butyl-4-hydroxyphenyl-propionyl) idrazine, 3-salicyloylamino-l, 2,4-triazole, bis (benzylidene) oxalyl-dihydrazide, oxanilide, isophthaloyl-dihydrazide, sebacoylbisphenylhydrazide, N, N'-diacetyladipoyl-dihydrazide, N , N'-bis (salicyloyl) oxalyl-dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide. 4. Phosphites, phosphines and phosphonites, for example, triphenyl-phosphite, diphenyl-alkyl-phosphites, phenyl-dialkyl-phosphites, trisnonylphenyl-phosphite, trilauryl-phosphite, trioctadecyl-phosphite, trimethyl-phosphine, tri-n-butylphosphine, triphenylphosphine , distearylpentaerythritol-diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl-pentaerythritol-diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-ter) -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 , tristearilsorbitan-triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene-diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-2H-dibenzo [d, g ] -l, 3,2-dioxaphosphocin, 6-fluoro-2, 4,8, 10-tetra-tert-butyl-12-methyl-dibenzo [d, g] -l, 3, 2-dioxaphosphocline, bis (2,4-di-tert-butyl-6-methylphenyl) methyl-phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl-phosphite, 2,2 ', 2"- nitrile [triethyl-tris-) 3,3 ', 5,5"-tetra-tert-butyl-l, 1-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3,3', 5 , 5'-tetra-tert-butyl-1, 1 '-biphenyl-2, 2'-diyl) -phosphite The following phosphites are especially preferred: tris (2,4-di-tert-butylphenyl) -phosphite (Irgafos ®168, Ciba Specialty Chemicals), trisnonylphenyl-phosphite and the phosphites having the structural formulas (a), (b), (c), (d), (e), (f) and (g): "j H3 (g) - Hydroxylamines, for example, N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine of hydrogenated tallow fatty acid amines. 6 Nitrones, for example, N-benzyl-a-phenylnitrone, N-ethyl-a-methylnitrone, N-octyl-a-heptylnitrone, N-lauryl-a-undecylnitrone, N-tetradecyl-a-tridecylnitrone, N-hexadecyl- a-pentadecylnitrona, N-octadecyl-a-heptadecylnitrona, N-hexadecyl-a-heptadecylnitrona, N-octadecyl-a-pentadecylnitrona, N-heptadecyl-a-heptadecylnitrona, N-octadecyl-a-hexadecylnitrone and N, N-nitronas dialkylhydroxylamines of hydrogenated tallow fatty acid amines. 7. Tiosynergists, for example, dilauryl- or distearyl-thiodipropionate. 8. Peroxide absorbers, for example, ß-thiodipropionic acid esters, for example, lauryl, stearyl, -myristyl or tridecyl esters, mercaptobenzimidazoles, zinc salt of 2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyl disulfide. , pentaerythritol-tetrakis (β-dodecylmercapto) -propionate. 9. Polyamide stabilizers, for example, copper salts combined with iodides and / or phosphorus compounds and salts of divalent manganese. 10. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallylcyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal and alkaline earth salts of higher fatty acids, for example, calcium stearate, zinc stearate, behenate or magnesium stearate, sodium ricinoleate, potassium palmitate, pyrocatecholium of antimony or zinc. 11. Nucleating agents, for example, inorganic fillers, for example, talc, metal oxides, for example, titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably alkali metals, organic acids, for example , mono- or polycarboxylic acids and their salts, for example, 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, succinate or sodium benzoate and also polymeric compounds, for example, ionic copolymers (ionomers). 12. Benzofuranones and indolinones, for example, according to U.S. Patent No. 4,325,863; U.S. Patent No. 4,338,244; U.S. Patent No. 5,175,312, U.S. Patent No. 5,216,052; U.S. Patent No. 5,252,643; DE-A-4 316 611; DE-A-4 316 622; DE-A-4 316 876; EP-A-0 589 839 or EP-A-0 591 102, or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5, 7-di- tert -butyl-3- [4- (2-stearoyloxyethoxy) phenyl] -benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy]] phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5, 7- di-tert-butylbenzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (3,4-dimethylphenyl) -5, 7-di-tert-butylbenzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one. 13. Additional additives, for example, plasticizers, lubricants, emulsifiers, pigments, flow agents, catalysts, fluorescent whitening agents, antistatic agents or blowing agents. The granule-forming additives and the mixture of additives described above are mixed together in a manner known per se, with, for example, so-called co-kneaders, twin-screw, co-rotating and counter-rotating extruders or extruders being suitable. single screw, which are suitable for mixing, kneading, incorporation, plasticization and homogenization of thermoplastic and curable plastics, for the dispersion of dyes and for other processes in the viscoelastic phase, for example, co-kneaders of types K and M , especially co-kneaders of type PR, which allows specific reductions of up to 1 kW per kg of mass processed per hour. The especially suitable apparatus are co-kneaders of the type PR of Buss AG, CH-Prattein, for example, the types of apparatus PR 100, 140, 200 or 300. According to the principle of the co-kneader, the work of mixing and Kneading is distributed among a plurality of small elements, for example, kneading teeth and helical blades. The operation is continuous or discontinuous, according to the lot. For continuous operation, it is important to have a uniform supply of material, which can be effected by means of a dosing device for liquids, melts or powdery or pasty materials. The conversion of the mixture of a workable mass is preferably carried out in a temperature controlled co-kneader, co-rotating or counter-rotating twin screw extruder or a single screw extrusion. By virtue of the thermal and mechanical (cutting) energy, the additives are mixed and processed into a workable mass. The housing and screw of the co-kneader can be individually heated in a plurality of zones, for example, by using double jacket heating. The temperature ranges from 20 ° C to 300 ° C are preferred. The filling zone is preferably cooled. The outlet nozzle is formed in a special manner and has a small number of holes, for example just one hole. For example, by being in the form of an injection head, strip or slot shaped nozzle, circular nozzle or spiral nozzle. The orifices in the outlet nozzles are from about 40 mm to about 200 mm in length, from about 6 mm to about 20 mm in width, or in the case of circular nozzles, they are from about 20 mm to about 150 mm in diameter. By leaving the outlet nozzle, the pre-formed extruded yarn mass is thus in a non-rigid state, for example, a plastic or plastic-crystalline state, which is capable of further formation. The extruded mass has a viscosity of about 1000 to 50,000 cPa.sec, preferably 1000 to 10,000 cPa.sec. The dough is cooled to a temperature at which it still remains workable. The mass can be discharged by means of a sliding channel that can be provided with a non-tack coating. As an alternative to the co-kneaders, screw extruders are used which can be provided with one or two screws (single screw extruders or multiple screw extruders, for example twin screw extruders), it being possible for the screws to be provided with the same or different winding (cutting elements and mixing components). The use of co-mashers is preferred. Reference is made to the apparatus described in Handbuch der Kunststoff extrusion, Editors F. Hensen, W. Knappe, H. Potent, Vol. 1, 1989, Grundlagen, ISBN: 3 -446-14339-4, and Vol. 2, 1986, Extrusions-anlagen, ISBN 3 -446-14329- 7. An analogous apparatus can be obtained from the manufacturers Brabender (DÉ), Werner &; Pfleiderer (DÉ) or Bühler (CH). While still in a manageable state, the created mass is then formed into granules by rolling, fixing, cooling and grinding. For lamination, a lamination method derived from the so-called calendering and known from the production of plastic films is used. The conventional calendering method consists of forming thermoplastic masses in endless strips by passing them through at least two rollers, called stretch or tightening rollers. The fixing process used in the method of the present invention differs from the calendering methods since, after rolling, the pre-formed plastic mass is then processed using linearly embossed forming rolls. The material is then fixed with a granular structure, which is necessary for the provision of predetermined breaking points for the crushing of the hardened fragments of the product mat. During the fixing, the transport can be carried out in a continuous band of steel of the Sandvik type, which is provided with a controllable drive and can be cooled by water that is sprayed on its lower part. The steel strip can have a bandwidth from about 200 mm to about 1500 mm and an effective cooling length from about 2 m to about 16 m. The lamination is carried out by passing the pre-formed material, to a plastic through two to three tightening rollers, the spacing between the rollers that can be adjusted and the smaller spacing that governs the size of the granules. The plastic material that has been laminated in this way is then processed by at least one, preferably two or three, rollers imparting a structure fixed to the material. In a preferred embodiment, these forming rolls have diagonal grooves running in opposite directions or grooves running longitudinally and transversely, which fix rhombic or square structures on the still plastic strip of material. There are at least two possible arrangements of the pinch rollers (high and low). When they are arranged in a high way, the plastic material that emerges from the outlet nozzle is guided upwards by the conveyor belt, making it possible for the conveyor belt to cool or heat up. When arranged below, the plastic material is guided downstream upstream of the first tightening roller. The tightening rollers and forming rollers can be arranged as in conventional calenders, which, as necessary, can be heated or especially cooled. The speed of rotation of the rollers must be matched to the flow of the paste (in order to avoid blockages). With regard to the cooling band located below, the rollers are mounted with their axis at an inclination of < 90 ° in the direction of flow. The rollers may also be provided with a non-tack coating. The fixed product strip is allowed to harden in a cooling band and at the end of the strip is divided into thick pieces using an additional roller. The resulting fragments are crushed to form granules along the lines fixed in a sieve granulator, for example, Frewitt type, GLA-ORV-0215 (4 mm sieve). The mesh size of the screen is matched to the size of the granules. The fine or finer granules are then sieved and separated from the granules. As an alternative to a screen granulator, the fragments formed along the fixed lines can be comminuted to form granules of the desired size in a roll crusher or in a roller mill. A combination of a roller crusher or roller mill with a screen granulator is also possible. The additive granules based on individual additives or mixtures of additives that can be produced in this way are suitable for stabilizing organic polymers against thermal degradation, oxidative or induced by light. They can be incorporated into polymers, for example, thermoplastics, especially thermosetting plastics, for example, based on polyolefins, polyesters, polystyrenes, polyacrylates, polyurethanes, polyamides, etc., in a manner known per se using known methods. The granules are also suitable for the preparation of so-called pre-mixes. The following examples illustrate the applicability and practicability of the method according to the present invention.

Example 1 50 parts of IRGANOX 1010 (tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate] of pentaerythritol) and 50 parts of IRGANOX 1098 (N) are mixed homogeneously in a batch mixer. , N > -hexane-1, 6-diyl-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide]). Using a dosing apparatus, the mixture is supplied to a Konti kneader (type PR100 7D) volumetrically at a yield of 50 kg / h. The kneading machine is controlled at a temperature of 100 ° C (entry to cooled to 20 ° C, tree 110 ° C). The temperature of the dough is 95 ° C. At a mass speed of 45 rpm (100 rpm = 150 kg / h), the product is extruded through a slot-shaped nozzle (dimensions 40 x 6 mm). The strand of the material is supplied by means of a cooled channel (20 ° C) to two cooled tightening rollers (20 ° C). The tightening rolls laminate the strand of the product in the plastic state (1000 to 10,000 cPas) on a strip 2 mm thick and approximately 10-15 cm wide that is deposited on a cooled metal strip (Sandvik cooling band; effective width 250 mm, effective length 4000 mm). Above the cooling band, two embossing rollers are mounted that fix a diamond structure on the still plastic strip of product. After fixing, the fixed strip of product hardens the cooling band and at the end of the band is divided into thick pieces. The fixed fragments are crushed to form the granules along the lines fixed in a sieve granulator (Frewitt type: GLA-ORV-0215; sieve 4 mm). The fine particles are then sieved. The granules according to the invention produced in this way have a uniform shape and exhibit advantageous properties of bulk material (Table 1).

Table 1 1) according to ISO 4324; 2) according to DIN 53492; according to Heubach test Example 2 Using a dosing apparatus, 100 parts of IRGANOX 1010 are supplied to a Konti kneader (type PR100 7D) in a volumetric manner at a throughput of 100 kg / h. The mixer is controlled at a temperature of 90 ° C (entry to cool at 20 ° C, shaft 90 ° C). The temperature of the dough is 70 ° C. At a shaft speed of 45 rpm, the product is extruded through a circular nozzle (diameter 24 mm). The material strand is supplied by means of a cooled channel (20 ° C) to two cooled tightening rollers (20 ° C). The tightening rolls laminate the strand of the product in a plastic state (1000 to 5,000 cPas) on a strip 2 mm thick and approximately 10-15 cm wide that is deposited on a cooled metal strip (Sandvik cooling band; effective width 250 mm, effective length 4000 mm). Above the cooling band, two embossing rolls are mounted that fix a rhombic structure on the still plastic strip of product. After fixing, the fixed strip of product hardens the cooling band and at the end of the band is divided into thick pieces. The fixed fragments are crushed to form granules along the lines fixed in a sieve granulator (type Frewitt: GLA-ORV-0215, sieve 4 mm). The fine particles are then sieved. The granules according to the invention produced in this way have a uniform shape and exhibit advantageous properties of bulk material (Table 2), especially in comparison with the powder used.

Table 2 1] according to ISO 4324; 'according to DIN 53492; 3) according to Heubach test EXAMPLE 3 5.2 parts of IRGANOX 1010, 25.8 parts of calcium stearate powder (calcium stearate DW®, FACÍ, IT) and 69 parts of TINUVIN®622 (dimethyl butanedioic acid ester, polymer with 4-5) are homogeneously mixed. hydroxy-2, 2,6,6,6-tetramethyl-1-piperidinetanol) in an MTI mixer. Using a dosing apparatus, the mixture is supplied to a Konti kneader (type PR100 7D) volumetrically at a throughput of 100 kg / h. The mixer is controlled at a temperature of 60 ° C (entry to cool down to 20 ° C; tree 60 ° C). The temperature of the dough is 50 ° C. At a shaft speed of 45 rpm, the product is extruded through a circular nozzle (diameter 24 mm). The material strand is supplied by means of a cooled channel (20 ° C) to two cooled tightening rollers (20 ° C). The tightening rolls laminate the strand of the product in the plastic state (1000 to 5000 cPas) on a strip 2 mm thick, approximately 10-15 cm wide, which is deposited on a cooled metal strip (Sandvik cooling band; effective 250 mm, effective length 4000 mm). Above the cooling band, two embossing rolls are mounted that fix a diamond structure on the still plastic strip of product. After fixing, the fixed strip of product hardens in the cooling band and at the end of the band is divided into thick pieces. The fixed fragments are crushed to form granules along the lines fixed in a sieve granulator (type Frewitt: GLA-ORV-0215, sieve 4 mm). The fine particles are then sieved. The granules according to the invention produced in this way have a uniform shape and exhibit advantageous properties of bulk material (Table 3), especially in comparison with the powder used.

Table 3 1J according to ISO 4324; 2) according to DIN 53492; 3 > according to Heubach's test

Claims (10)

1. CLAIMS 1. Method for producing low-powder granules of polymer additives or polymer additive mixture, characterized in that the granule-forming polymer additives are mixed together, the mixture is converted into a workable mass and pressed through. a hole, and the strand-type pre-formed extruded mass is cooled and still in a workable state, is formed into granules by rolling, fixing, cooling and grinding.
2. 2. Method according to claim 1, characterized in that the phenolic polymer additives of the formula are mixed together as granule-forming polymer additives: wherein, independently of one another, one of Ri and R2 is hydrogen, a substituent selected from the group Cx-Ci8alkyl, phenyl, (C? -C4alkyl)? _3f enyl, f-C-C3alkyl, (C? -Calkyl) )? 3-phenyl-C? -C3alkyl, C5-C? 2-cycloalkyl and (Cx-C alkyl) _3C5-C? 2-cycloalkyl or a group of the partial formula - (A), where Ra is hydrogen or a substituent selected from group C ? -Calkyl, halogen and sulfo; and the other is a substituent selected from the group C? -C18alkyl, phenyl, (C? -C4alkyl)? _3phenyl, phenyl-C? -C3alkyl, (C? -C4alkyl)? _3phenyl-C? -C3alkyl, C5-C12cycloalkyl and (C? -C4alkyl)? -3C5-C12cycloalkyl or a group of the partial formula (A), wherein Ra is as defined; R3 is hydrogen or methyl; m is the number zero or 1; and n is an integer from 1 to 4; where, when n is the number 1, m is zero or 1 and Y denotes: a monovalent substituent -0-Y? or -N (-Y2) 2, wherein Yi is C5-C45alkyl, C3-C45alkyl interrupted by at least one oxygen atom, C5-C2-cycloalkyl, C2-C12alkenyl, a substituent of the partial formula -CH2-CH ( 0H) -CH2-0-C (= 0) -Rb, (B), wherein Rb is hydrogen, C? -C8alkyl, C3-C5alkenyl or benzyl, a substituent of the partial formula -CH2-CH2-0-Rc (C), wherein Rc is hydrogen, C -C2 alkyl, C5-C? 2-cycloalkyl or phenyl, a substituent of the partial formula -CH2-CH2-0-CHRd-CHRe-C (= 0) -O-Rf ( D), wherein one of Rd and Re is hydrogen or methyl and the other is methyl, and Rf is hydrogen or C? -C24alkyl, a substituent of the partial formula wherein Rx and R2 are as defined above, or a substituent of the partial formula -CH2-CH2-0-CH2-C (= 0) -0-Rg (F), wherein Rg is hydrogen or C? -C2alkyl; and Y2 is hydroxy-C2-C4alkyl; or, when n is the number 2, m is zero and Y is a bivalent group of the partial formula -0-CxH2x-0- (G), where x is an integer from 2 to 20, -0- (CH2- CH2-0) y-CH2-CH2-0- (H), where y is an integer from 1 to 30, -0-CH2-CH2-S-CH2-CH2-0- (I), -0- CH2-CH = CH-CH2-0- (K) or -NH- (CH2) 2-NH- (L), where z is zero or an integer from two to ten; or when n is the number 3, m is zero and Y is a trivalent group of the partial formula wherein Rh is C? -C24alkyl or phenyl, or when n is the number 4, m is zero and Y is the tetravalent group of the partial formula
3. 3. Method according to claim 1, characterized in that the phenolic polymer additives of the formula are mixed together as granule-forming polymer additives: wherein, independently of each other, one of Rx and R2 is hydrogen or C? -C alkyl and the other is C3-C4alkyl; x is zero (direct link) or an integer from one to three; and Y is C8-C22alkoxy or a group of the partial formula wherein, independently of one another, one of Rx 'and R2' is hydrogen or C? -Calkyl and the other is C3-C4alkyl; x is zero (direct link) or an integer from one to three; and is an integer from two to ten and z is an integer from two to six.
4. 4. Method according to claim 1, characterized in that the granule-forming polymer additives are converted into a workable mass in a heatable co-masher.
5. Method according to claim 1, characterized in that the workable mass is extruded from the coamasador through a circular nozzle or slot-shaped nozzle and the preformed strand-like mass is subjected to further processing.
6. 6. Method according to claim 1, characterized in that the pre-formed, plastic mass is processed by tightening rollers having a smooth and polished surface and then the forming rollers provided with embossing lines.
7. Method according to claim 1, characterized in that the forming rollers are provided with grooves.
8. 8. Method according to claim 1, characterized in that the transport and cooling and solidification are carried out in a continuous steel strip.
9. Method according to claim 1, characterized in that the components of the granule-forming polymer additives are fed into the co-hammer in liquid or solid form or in molten form.
10. 10. Method according to claim 1, characterized in that the fixed product mat is crushed to granule size in a screen granulator.