MXPA99008965A - Preparation of low-dust stabilisers - Google Patents

Abstract

A description is given of an extrusion process for the preparation of a low-dust stabiliser, using a subcooled melt as granulation liquid, as well as of novel amorphous modifications of different stabilisers, including 2,2'-methylenebis(4-[1,1,3, 3-tetramethylbutyl]-6-benzotriazol-2-yl-phenol), and of the&bgr;-crystalline modification of 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole and of the preparation thereof. The novel process affords products which are easy to handle and which are flowable, and the novel modifications have advantages as regards their preparation, processing and their use as stabiliser.

Description

PREPARATION OF LOW-STABILIZERS DUST CONTENT The present invention relates to a process for the preparation of stabilizers of low content of powder, by extruding a sub-cooled melt, to the use of the products of this process to stabilize organic polymers, to novel amorphous modifications, for example of 2,2'-methylenebis - (4- [1,1,3,3-t etrame-il-butyl] -6-benzotriazo-2-yl-phenol), to a novel crystalline modification of 2- (2-hydroxy-3,5-diter-butylphenyl) -5-chloro-benzotriazole, to a process for its preparation and processing as well as to compositions stabilized therewith. The development of low-dust stabilizers and therefore generally easier to handle has been sought for some time; specific stabilizers among others have been mounted on inorganic substrates (for example in US-A-5238605). GB-A-2267499 describes the preparation of a mixture of tetraalkylpiperidine stabilizers of high and low molecular weights upon mixing in a molten state. US-A-559-7857 discloses a process for the preparation of low-dust stabilizers by extruding a calcium stearate melt; JP-A-59-104348 and EP-A-565184 also propose to extrude a fusion. DE-A-19541242 proposes the formation of pellets with a mixture consisting of crystalline and fused plastic additives. I The use of a regular melt during extrusion is only possible to a limited degree due to its low viscosity. Amorphous modifications of individual stabilizers and their use to stabilize organic polymers have already been described among others in EP-A-278579, US-A-4683326, EP-A-255743, US-A-5373040, US-A-5489636 , JP-A-59-104348, US-5574166-. They are usually prepared by rapidly cooling the melt to avoid crystallization. EP-A-278579 describes the preparation of a partially crystalline stabilizing mixture consisting of amorphous tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane and a crystalline organic phosphite to the sub- cool the fusion. Patent EP-A-514784 describes the extrusion of tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionyloxy-methyl] methane and its mixing with inorganic salts of fatty acid salts at temperatures the fusion range. Surprisingly, it has been found that the metastable state, which is passed during the preparation of amorphous low molecular weight stabilizers, the subcooled melt, is excellently suitable for use as a liquid or granulation binder during extrusion. It is notable that the formation of crystalline modifications of low molecular weight stabilizers is unexpectedly inhibited, making it possible to process the plastic extrusion compositions into granules by conventional methods. Accordingly, this invention relates to a process for the preparation of a low-powder stabilizer, which comprises extruding a subcooled melt of a stabilizer having a molecular weight of 200 to 1500 g / mol, or the plastic composition of the mixture consisting of the sub-cooled fusion of the stabilizer and a crystalline stabilizer and / or other usual additives. The plastic composition therefore consists of a subcooled melt as a homogenous continuous phase and when appropriate, of additional components dispersed therein (one or more dispersed phases). The processing for commercially stable, low-dust, storstable forms, for example, for pelleting, pelleting, melt granulation and compound formulation, is thereby made substantially easier or possible in fact. The molding of the product for example can also be carried out before or during the cooling process, by dividing the subcooled melt or the mixture, for example by dripping in the liquid state or by dividing in the plastic state with subsequent cooling. The process of this invention thus also encompasses a process for granulating a stabilizer, which comprises extruding and dividing a subcooled melt of the stabilizer or the plastic compound which "consists of the mixture of the subcooled melt of the stabilizer and the crystalline stabilizer and / or other usual additives." Solidification after extrusion gives a stabilizer of low powder content, for example as granules This invention also relates to the granules obtained by the novel process as well as the use of a subcooled melt to extrude a stabilizer or mixture of stabilizers, in particular for pelleting, granulation Fusion or composite formulation The subcooled fusion is single phase and according to this only has a simple vitreous transition temperature; however, it may consist of one or several chemical compounds and preferably consists of 1 to 3 main components. It will be understood that the main components are those compounds, the proportion of which in the subcooled melt is 10% by weight or more, preferably 30% by weight or more. Also importantly, it is a subcooled melt consisting primarily, ie usually up to 60% by weight or more, preferably up to 70% by weight or more, of 1 chemical compound (the weight is always based on the total weight _ i * of the homogeneous subcooled melt). The amount of tetrakis [3- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionyloxymethyl] methane in the subcooled melt is preferably less than 80% by weight, more preferably 0-60% by weight. weight. A particularly important process of this invention is that wherein tetrakis [3- (3, 5-diter-butyl-4-hydroxy-phenyl) propionyloxymethyl] methane is not a major component of the sub-cooled fusion. The molecular weight of the chemical compounds constituting the subcooled melt (main components) is usually 300-1200 g / mol, preferably 300-1000 g / mol, particularly preferably 500-1000 g / mol. These chemical compounds are usually one or more organic compounds, for example hydrocarbons containing 6 to 100 carbon atoms and, when appropriate, 1 to 30 hetero atoms such as O, N, S, P, halogen. The melting point (mp) of the chemical compound, which forms a major component, preferably any component present at more than 5% by weight, is usually 130 ° C or higher, preferably 140 ° C or higher, more preferably 170CC or more. above, and the glass transition temperature (TG) is in the range of 10-120 ° C, preferably 20-100 ° C. The ratio of vitreous transition temperature (TG) to melting point (m.p.) each measured in degrees Kelvin (K), preferably in the range of 0. 6 to 0.9; more preferably in the range of 0.65 to 0.85. The compounds that form the subcooled fusion are usually light stabilizers or antioxidants, for example those mentioned in the list given below under items 1, 2 and 4, provided they meet the established criteria regarding molecular weight, point of fusion and vitrea transition temperature. They preferably belong to the class consisting of UV absorbers, sterically hindered amines (HALS), phenolic antioxidants, phosphites, phosphonites, lactones. In the novel process, it is generally possible to use these compounds which, by themselves or as mixtures, are also obtained in simple phase amorphous upon cooling of the melt. The following compounds are preferably used in the novel process: 1) 2,2'-methylenebis (4- [1,1,3,3-tetramethyl-butyl] -6-benzotriazol-2-yl-phenol) (No. Reg. CAS 103597-45-1) of the formula 2) bis (2-methyl-4-hydroxy-5-tert-butylphenyl) sulfide (CAS No. 000096--69-5), 3) (CAS No. 069851-61-2), 4) N, N'-bis (3- [3 ', 5'-di-tert-butyl-4'-hydroxyphenyl] -propionyl) hexamethylenediamine (No. of CAS No. 023128-74-7), 5) 1, 3, 5-trimethyl-2,4,6,6-trist (3 ', 5-di-tert-butyl-4'-hydroxy-benzyl) benzene (No Reg. CAS 001709-70-2), 6) 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxy-benzyl) -1, 3, 5-triazin-2, 4 , 6 (1H, 3H, 5H) trione (CAS reg. 027676-62-6) (CAS No. 032687-78-8), 8) 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethyl-benzyl) 1, 3, 5-triazine 2, 4, 6- (1H, 3H, 5H) triona (CAS Reg. No. 040601-76-1), 9) di (1,2, 2, 6, 6-pentamethylpiperidin-4-yl) -2 - (3, 5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate (CAS No. 063843-89-0), 10) 2- (2'-hydroxy-3 ', 5) '-bis (1,1-dimethylbenzyl) phenyl) benzotriazole (CAS Reg. No. 070321-86-7) of formula 11) 2- (2 '-hydroxy-3', 5 '-di- er-bu ilphenyl) benzotriazole (Reg. No. CAS003846-71-7); 12) isomeric mixtures (CAS No. 181314-48-7) consisting of about 85% by weight of 5,7-di-tert-butyl-3- (3,4-dimethyl-phenyl) - (9d) ) -2 (3H) -benzofuranone and approximately 15% by weight of 5,7-di-tert-butyl-3- (2,3-dimethylphenyl) - (9d) -2 (3H) benzofura none; 13) pentaerythritol-tetrakis (3- [3 ', 5' -di-tert-butyl-4 '-hydroxyphenyl] propionate) (CAS No. 006683-19-8); 14) 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole (CAS No. 3864-99-1) 15.).

(CAS No. 080410-33-9); 16) tris (2 { 4-di-tert-butylphenyl) phosphite (Reg.

CAS031570-044); 17) (CAS No. 26741-53-7)18] (CAS No. 37042-77-6); 19) 2- [2 '-hydroxy-3' - (a, a-dimethylbenzyl) -5 '- (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole of the formula (CAS No. 073936-91-1) The following table gives the molecular weight of (Mw), melting point (mp, DSC + 4 ° C / minute), enthalpy of fusion (? H), temperature of glass transition (Tg; DSC + 20 ° C / minute) and preferred processing temperature (Tp) of these compounds: Compound Mw pf ? H Tg (° C) Tp (° C) (a / mol) (° C) (J / cr) approx. 1) 658 197 86 70-80 90-140 2) 358 161 113 25-35 40-60 3) 594-8 177 93 55-65 70-100 4) 636.9 160 96.5 50-60 70-130 ) 775"179/243 * 200/65 * 90-100 105-125 6) 784 220 75 105-115 115-140 7) 5 3 200/229 * 50/120 * 65-75 75-100 8) 699 158 20.5 110-120 120-155 9) 685 148 80 40-50 55-145 ) 447.6 139 84 35-45 55-100 11) 323 -4 154 88.5 15-25 25-40 12) 350.5 132 90 20-30 40-80 13) 1177.6 105- • 125 * 50-72 * 40-55 65-95 14) 357.9 157 80 20-30 30-40 ) 1465 203 46.5 105-115 130-200 16) 646.9"Í86 71 35-45 50-70 17) 604 172 65 45-55 65-80 18) 552 163 apr.120 50-60 70-150 Compound Mw p.f. ? H Tg (° C) Tp (° C) (a / mol) (° cj (J / g) approx. 19) 441.4 113 64-65 30-40 50-100 * different crystal modifications The subcooled fusion is conveniently obtained by rapidly cooling a regular melt, the final temperature is below the melting point (mp) of the main component, preferably lower than the regular melting point (mp) of the component which has the lowest melting point (usually referred to as the melting point only below). The final temperature of preference is in the range of the processing temperature set forth below. The cooling process can be carried out in a manner known per se, for example by introducing a melt to the cooled extruder, melting the stabilizer in the extruder and then transporting the melt to a corresponding cooled zone, or when preparing the sub-cooled melt. outside the extruder. The fusion may result directly from the synthesis of a compound or from melting one or more compounds. The subcooled melt can also be obtained by rapidly melting a solid amorphous compound at a temperature from the vitreous transition temperature to the melting point of the crystal modification, preferably in the range of the processing temperature. Depending on the cooling method or cooling rate, the melt can also be processed to an amorphous or partially amorphous product, for example, pellets, using a melting spindle or extruder. It has also been found that the subcooled single phase melt can surprisingly also contain a lower proportion of compounds, for example up to 40% by weight, in particular up to 30 or 20% by weight, in dissolved form, the transition temperature vitrea (TG) of * which is less than 10 ° C, meaning that they can not be obtained in an amorphous form by cooling processes using usual cooling temperatures up to about 0 ° C; the precondition is that the vitreous transition temperature of the resulting phase is above 10 ° C, in particular above 20 ° C. These compounds usually also belong to the group of light stabilizers or antioxidants as indicated above for the compounds that form the subcooled melt. The subcooled melt and components that can be dispersed there form the extrudable plastic composition. The subcooled melt component in the novel extrusion is preferably from 5 to 100% by weight, more preferably from 20 to 100% by weight, in particular from 50 to 100% by weight of the plastic composition. Other dispersed components, if present, are preferably crystalline at the processing temperature. Additional dispersed components are usually conventional additives, for example of the classes and products mentioned below, as possible coadditives. It is preferred to use in particular phenolic antioxidants, organic phosphites or phosphonites as well as sterically hindered amines. It will be understood in this connection, that extrusion is any process that guarantees a transport of the plastic composition often by means of a spindle with convenient tempering. The plastic composition is usually mixed and / or further molded after passing through a hardened zone, for example to pellets or threads. The plastic additives (stabilizers) are advantageously processed in a single or double screw extruder. These extruders are known in the plastics processing industry and are distributed on the market for example by Buss (CH), Brabender (DE), Werner and Pfleiderer (DE) or Bühler (CH). Then or also while the still soft extruded products are cut and after passing through a perforated die or plate, the granule particles are often cooled. Cooling can be carried out in the form of wet cooling with water (for example in water, by a water film, water ring, etc.) or preferably with air (for example air film, air vortex, etc.). .,) or also combined. Cooling with water requires subsequent dehydration and drying (preferably in a vortex dryer or fluidized bed dryer). The technical implementations of these cooling methods are known. Preferably, granulation is carried out while the material is still in the plastic state, before the current cooling stage, in contrast to the extrusion milling and granulation process usually in the state of the art. The processing temperature of the plastic composition is preferably about the same as between the regular melting point (m.p.) and the glass transition temperature (TG) of the homogeneous phase. The processing temperature is preferably in the range from TMIN to T ^, where with (p.f.) - (TG) =?: TMIN = TG + 0.2? T ^ = TG + 0.6?; particularly preferably: MIN = TG + 0.3? TMAX = TG + 0.5? In other aspects, this invention relates to granules obtained by the novel process as well as to the use of a subcooled melt of a stabilizer for extrusion, in particular for pelletization, melt granulation or compound formulation. Depending on the conditions of implementation and cooling, the novel process generates a crystalline, partially crystalline or completely amorphous product. Accordingly, this invention also relates to a single phase amorphous stabilizer comprising two or more compounds having a molecular weight in the range of 300-1,000 g / mol. Novel amorphous modifications This invention also relates to novel amorphous forms of stabilizer, known hitherto only in its crystalline modification, ie the compounds * 1) 2,2'-methylenebis (4 [1, 1, 3, 3-tetramethylbutyl ] -6-benzotriazol-2-yl-phenol) (GAS Reg. No. 103597-45-1) of the formula 2) bis (2-methyl-4-hydroxy-5-tert-butylphenyl) sulfide (CAS No. 000096-69-5), 3) (CA-reg. No. 69851-61-2), 4) N, N '-bis (3- [3', 5 '-di-tert-butyl-4' -hydroxyphenyl] -propionyl) examethylenediamine (No. Reg. CAS 023128-74-7), 5). 1, 3, 5-trimethyl-2,4,6-tris (3 •, 5 '-di- er-butyl-4'-hydroxybenzyl) -benzene (CAS Reg. No. 001709-70-2) 6 1.3, 5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4 < 6- (1H, 3H, 5H) friona (CAS No. 027676-62-6) 7) (CAS no. CAS 032687-78-8) 8) 1, 3, 5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1, 3, 5-triazine-2 , 4, 6- (1H, 3H, 5H) friona (CAS No. 040601-76-1) 9) di (1,2, 2, 6, 6-pentamethylpiperidin-4-yl) -2- ( 3, 5-di-tert-butyl-hydroxybenzyl) -2-n-butylmalonate (CAS No. 063843-89-0), 10) 2- (2'-hydroxy-3 ', 5' - bis (1,1-dimethyl-ylbenzyl) -phenyl) -benzotriazole (CAS Reg. No. 070321-86-7) of the formula 11) 2- (2 '-hydroxy-3', 5'-di-tert-butyl-enyl) -benzotriazole (Reg. No. CAS003846-71-7); 12) isomeric mixture of 5, 7-di-tert-butyl-3- (3, 4-dimethyl-phenyl) - (9d) -2 (3H) benzofuranone and 5,7-di-tert-butyl-3- ( 2, 3-dimethylphenyl) - (9d) -2 (3H) -benzofuranone; 14) 2- (2-Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, synonymous with 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) -phenol ( CAS No. 3864-99-1), of the formula (CA-reg No. 37042-77-6) Compound 12, is an isomeric mixture, has reg. No. CAS181314-483-7 and consists of about 85% by weight of 5,7-di-tert-butyl-3- (3,4-dimethyl-il-enyl) - (9d) -2 (3H) -benzofuranone and about 15% by weight of 5,7-di-tert-butyl-3- (2,3-dimethylphenyl) - (9d) -2 (3H) -benzofuranone. These compounds, at the same time, are particularly preferred compounds for use in the extrusion process described at the beginning. The compounds mentioned are effective for stabilizing organic material against the harmful action of light, heat and oxygen. The compound (1) and its use has been described among others in US-A-4812498, US-A-4948666, US-A-4681905, and its preparation in US-A-5229521 and US-A- 4812498; compound (14) is particularly effective as a UV absorber and its preparation is described inter alia in US-A-4001266, US-A-4041044, US-A-4219480, US-A-4230867 and US-A-4999433; the known modification of the compound (14) has in pure form, a melting point of about 156 ° C and is commercially available under the trade name Tinuvin ™ 327. The novel amorphous forms of the compounds 1-12, 14 and 18 give a X-ray diffraction diagram free of lines, for example with Cu-ka radiation. They are also characterized by their vitreous transition temperature (Tg) which for example in compound 14, is in the range of 20-30 ° C in particular of 20-25 ° C. The preparation of the amorphous form of the compounds 1-12, 14 and also 18 is conveniently carried out by the novel process or in particular by rapid quenching of the melt, preferably starting from a temperature a little above the melting point or top, typically 1-30 ° C above the melting point, at a temperature lower than the temperature and vitreous transition (Tg) for example 20-50 ° C lower than Tg. This can be done in known manner, for example by application to a cooled surface (for example a cooling conveyor), introduction to a cooled non-reactive liquid or by cooling in a gas stream, for example with air or nitrogen. The temperature of the solid or liquid cooling medium of X preferably is less than 100 ° C, in particular lower than 50 ° C, for example in the range of 0-50 ° C, preferably in the range of 5-20 ° C; the temperature of the gas stream used for cooling is preferably 20 ° C or lower, for example in the range of 0-20 ° C, preferably 0-10 ° C. The preparation of the amorphous form of the compound 14 is conveniently carried out by rapidly cooling a melt of the compound, preferably starting at a temperature of 159 ° C or more at a temperature of 20 ° C or more. This can be done in known manner, for example by application to a cooled surface, introduction into a cooled non-reactive liquid or by cooling in a gas stream, for example with air or nitrogen. The temperature of the cooling medium is preferably below 20 ° C, in particular below 10 ° C, for example in the range from -10 to + 15 ° C, preferably from -5 to 5 ° C. The amorphous solid thus obtained can be comminuted by known methods, for example by milling to any desired particular size, the product temperature being kept conveniently lower than the glass transition temperature. The novel amorphous modifications are distinguished from crystalline modifications by a number of advantages, among others in preparation, further processing and use. Rapid cooling of the melt below the glass transition temperature, for example, results in the heat of crystallization not being released (in the case of compound (1) approximately 85-88 J / g), so that it requires removal less energy by cooling and can reduce the cooling time of the products sensitive to oxidation.The incorporation and distribution in the material to be stabilized is further facilitated by the lack of heat of fusion.The novel modifications dissolve more easily and homogeneously On the other hand, in organic solvents such as lubricating oils, lubricants, urethanes, prepolymers and others, and in the organic material to be stabilized, for example the organic polymer, it is possible to achieve a more uniform distribution in the substrate to avoid inhomogeneity as well as obtain good processability and excellent effectiveness. The plastic of the sub-cooled fusions makes possible the processing of the extruder, wherein either the pure amorphous form can be employed or a mixture consisting of the novel amorphous modification and the usual crystalline form and / or other usual additives. This invention therefore also relates to a mixture consisting of a subcooled melt or of an amorphous solid of one or more compounds of 1-12, 14 and 18, of a crystalline compound and / or a usual stabilizer, the proportion of the novel amorphous modification is preferably from 5 to 100% by weight, in particular from 20 to 1005 by weight, of the mixture and in which in particular the usual stabilizer can already be solid or also amorphous.

Amorphous mixtures which usually have the same advantageous application properties as simple amorphous compounds are particularly important in this respect. Many low molecular weight compounds, such as those mentioned above, are soluble in each other in the melt and are capable of forming eutectic mixtures. In mixtures, the component having the lowest melting point can serve as a solvent for one or more other components. In this way, it is possible to obtain single-phase amorphous mixtures of multiple components that are distinguished by having only one glass transition temperature Tg. Due to the interaction of the individual compounds, the mixture physically has a novel amorphous structure, the Tg value from which it can be derived from Tg values of the individual amorphous modifications and their concentration. Accordingly, it is possible to selectively prepare phase-specific micro-homogeneous mixtures by mixing these compounds with each other or by mixing other low molecular weight additives, such as compounds Nos. 13, 15, 16, 17 which are you know they also have an amorphous modification. It is even possible to use some additives which are only known in crystalline form, the Tg of which is well below 15 ° C (for example the compound 2, 2, 6,6-tetramethylpiperidin-4-yl) sebacate) in a small quantity. The vitreous transition temperature here can be adjusted preferably between 40 to 100 ° C by a right combination of the compounds to ensure on the one hand an amorphous stabilizer that melts easily and at low temperature (energetically favorable, advantageous for certain applications) and on the other hand, good storage stability. Novel crystal modification of compound No. 14 It has also been found that a novel crystalline modification (β-form, high temperature modification) can be obtained by balancing 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5- chlorobenzotriazole (compound No. 14) in a specific temperature range. This crystalline modification is distinguished from the conventional crystalline form by improved performance properties, such as higher gross density and compacted crude density, improved fluidity, dispersability in the substrate and less dust release when handled and this modification also constitutes a object of this invention. The physical properties of the novel beta-modifications of compound 14 have a number of differences compared to the alpha modification, some of which have been found as follows: modification-alpha modification-S melting point "156 ° C 158 ° C contact angle of benzyl alcohol 24.5 ° 19.5 ° loose gross density 0.39 kg / 1 0.49 kg / 1 density of compacted volume 0.72 kg / 1 0.79 kg / 1 compressibility 46% 38% a.-angle of rest 54 ° 50 ° factor of flow (according to Jenike) 1.6 2.6 The following table provides the interplanar spacings determined by X-ray diffraction (Cu-k alpha radiation, measurement of dust power diagrams in transmission geometry using a Guinier camera) the well-known alpha form as well as for the novel beta crystalline form (d, given in ?? = 10_10m) and reflection intensities (visually determined) alpha modification beta modification intensity intensity dTAl ad 16. 0 medium 16.1 weak 9.8 force 9.4 force 8.6 very weak 8.0 very strong 8. 0 very strong 7.2 weak 6.4 weak 5.88 weak modification alpha beta modification C-JÁ] intensity of intensity . 99 medium 5.61 medium 5.61 weak 5.42 weak 5.43 weak 5.37 weak 5.07 very "weak 5.22 very weak 4. 83 force 4.84 force 4.58 force 4.69 force 4.55 force 4.49 medium 4.30 weak 4.18 very weak 4. 04 very weak 4.15 very weak 3. 99 strength '3.94 very strong 3. 87 very strong 3.79 medium 3.71 very weak 3.63 very weak 3. 63 very weak 3.62 very weak 3. 20 very "weak" 3.43 very weak 3. 13 medium 3.34 very weak! 3.10 very weak 3.23 medium 3.04 weak 3.20 very weak 2. 94 medium 3.09 very weak 2. 90 very weak 3.03 medium 2.92 weak Characteristics of the ß form, for example are the reflections that correspond to the interplanar spacings (d) at d = 9.4 -10 ~ 10 m; ad = 4.69-10"10 m; d = 3.94-10" 10 myd = 3.79-10"10 m (medium or high intensity) Modification of the invention of compound 14 can be obtained by equilibrating the compound at a temperature above 70 ° C, preferably above 95 ° C, more preferably above 106 ° C and then cooled rapidly, preferably at 15-20 ° C or lower Suitable for equilibrium are for example tempering as well as dissolution and / or melting processes with mixing for example during extrusion in the novel process Crystallization before the cooling process gives the beta-crystalline form, the amorphous form is obtained in another way The preparation of the beta-crystalline form is conveniently carried out by crystallization of the crystalline form. compound 14 about 70 ° C, typically about 95-106 ° C, preferably about 106 ° C, or upon tempering the alpha-crystalline form in the temperature range of 70 ° C, preferably 95 ° C, more preferably 106 ° C, and at a melting point of the alpha-crystalline form typically in the range of 106 ° C to 155 ° C, preferably 110 ° C to 150 ° C, with subsequent rapid cooling of the beta crystalline form which is typically obtained at 50 ° C or less, preferably at 15 ° C. -30 ° C or at room temperature (20-25 ° C) or lower.

Crystallization can be carried out by the usual methods of the art, for example by crystallization from a subcooled solution or melt of the compound which is maintained below the melting point - or by cooling a melt. The process of cooling a temperature above 70 ° C, such as above 95-160 ° C or about 156 ° C to 50 ° C, or * room temperature, may proceed in a continuous or discontinuous manner, the cooling rate is slowed down or it stops in the range of 95 to 156 ° C, preferably of 106-150 ° C. The cooling process can usually also be combined with the molding of the compound, for example granulation or pastillation. Typical examples of specific processes are processing to make fluid or fluid bed granulation. Parallel, tempered, the compound is heated either directly or with the addition of a suitable solvent, for example, or a mixture of xylene and butanol with a sufficiently high boiling point, conveniently for about 20 minutes to about 24 hours. at a temperature in the aforementioned range. The cooling is then carried out as indicated above. Suitable solvents, for example, are those having a boiling point which is markedly above 95 ° C, in particular above 106 ° C, at normal pressure, preferably alcohols or hydrocarbons such as toluene xylene, or mesitylene or mixtures thereof. The use of solvents having lower boiling points is also possible, in which case the pressure is increased in a useful manner such that the solvents remain liquid in the aforementioned temperature range. These solvents can subsequently be removed more easily than the high-boiling solvents mentioned at the beginning. When a solvent is used, the compound 14 can also be completely or partially dissolved, and the crystallization of the dissolved components can then be achieved, inter alia, by slight cooling of the lower range of the aforementioned temperature range, for example 70-100 °. C, 95-110 ° C or 106-120 ° C and / or by removing the solvent by distillation. The beta-crystalline product may if required be carried to any other desired form of particle size and presentation by known methods, such as milling, compression, extrusion or granulation. The use of mixtures of the novel modifications with each other and with the usual alpha-crystalline modification also has the advantages of the aforementioned type versus the use of pure crystalline modification. The novel mixture consisting of different modifications of the compound 14, preferably containing at least 40% by weight, preferably at least * 0% by weight, more preferably at least 80% by weight, of the beta-crystalline and / or amorphous form and not more than 50% by weight, preferably not more than 20% by weight, more preferably not greater than 10% by weight, of foreign or foreign components (each based on the total weight of the mixture). * Another advantage of the beta-novel modification of compound 14 consists in the easiest and most homogeneous solubility on the one hand of organic solvents such as lubricating oils, lubricants, urethanes, prepolymers and on the other hand the organic material to be stabilized can by example the organic polymer such as a more uniform distribution is achieved, avoiding inhomogeneity and excellent effectiveness is guaranteed. The "novel modifications of the compound 14 are particularly convenient for stabilizing organic materials, for example in particular the organic polymers mentioned below, against damage by light, oxygen or heat.The novel modifications are very particularly convenient as light stabilizers (UV absorbers). Stabilization- of color of compound No. 13 Amorphous pentaerythritol-tetrakis (3- [3 ', 5' -di-tert-butyl-'-hydroxu phenyl] propionate) (CAS eg No. 006683-19-8; Compound No.13), which is usually obtained as a colorless powder during synthesis, darkens rapidly during storage, the product takes a greenish to yellowish tint (greening), depending on storage conditions, in particular exposure to light and oxygen, this unwanted effect usually occurs after about 4-12 weeks.The use of mixtures comprising this compound in the novel extrusion process surprisingly shows that in the case of certain additives, the color stability of the amorphous compound 13 is improved markedly and the effect of greening is avoided or at least slowed down a lot.It is important in this aspect that a micro-homogeneous amorphous mixture is obtained.In another of its aspects, this invention therefore also relates to a method for stabilizing the color of pentaerythritol -tetraquis (3 - [3 ', 5'-di-tert-butyl-4'-hydroxyphenyl] -propionate) amorphous, comprising mixing a stabilizer of the class consisting of phosphites, organic phosphonites and / or benzofuran-2-ones to a fusion of pentaerythritol-tetrakis (3 - [3 ', 5' -di-tert-butyl-4 '-hydroxyphenyl] propionate) and rapidly cool the mixture thus obtained. The use of a stabilizer of the class consisting of phosphites, organic phosphonites and / or benzofuran-2-ones to 'stabilize the color of pentaerythritol-t-etraquis- (3- [3', 5 '-diter-butyl-' Amorphous is another object of this invention. Compound No. 13 stabilizing a color in this manner forms a microhomogeneous phase together with the stabilizer. The stabilizing component (phosphite, organic phosphonite and / or benzofuran-2 -one) in this phase of preference is at least 1% by weight, typically 1-95% by weight, in particular 5-90% by weight, preferably 5 to 55% by weight. The cooling process which gives the color stabilized compound No. 13, partially amorphous, preferably single-phase amorphous, can be carried out in a manner described above for the preparation of the novel amorphous modifications. In this regard, organic phosphites or phosphites to be understood mean the compounds of the formula P (OR) 3, wherein the radicals R are hydrocarbon radicals which may contain heteroatoms and wherein a maximum of two of the three radicals R may additionally be hydrogen atoms. Hetero-atoms are all atoms except for carbon and hydrogen, in particular the atoms N, 0, F, Si, P, S, Cl, Br, Sn and I.

Phosphonites are esters of the phosphonous acid of the formula P (OR) R wherein R has the meanings given above or can be halogen. Phosphites or phosphonites preferably used in the process of the invention are those corresponding to one of the formulas (1) to (7), (1) RJ -Y '-P (OR'2) (0R'3), ( 2) A '- (X'- P (OR' 2) (OR '3)) n.; where the indices are integers, and n 'is 2,3"or 4, p is 1 or 2, q is 2 or 3, r is 4 to 12, and is 1, 2 or 3, and z is 6; , if n 'or q is 2, it is alkylene with 2 to 18 carbon atoms, alkylene with 2 to 12 carbon atoms which is interrupted by -S-, -O- or -NR'4_, a radical of one of the formulas or phenylene; A1, if n 'o- q is 3, e.s a radical of the formula -CrH2rl-; A ', if n "is 4, is the radical of the formula C (CH2) 4; A "has the meaning of A ', if n1 is 2; B' is a radical of the formula -CH2_; -CHR'4_; -CRJR'4-; -It is a direct bond; or cycloalkylidene with 5 to 7 carbon atoms; carbon; or cyclohexylidene which is substituted by 1 to 4 alkyl radicals with 1 to 4 carbon atoms at positions 3, 4 and / or 5; D ', if p is 1, is methyl and if p is 2, it is -CH2OCH2 ~ E1, if y is 1, is alkyl containing 1 to 18 carbon atoms, a radical "of the formula -OR'i or halogen, - E ', if y is 2, is a radical of the formula -0 -A "-0-; E1, yes and is a radical of the formula R! 4_C (CH20) 3-; Q 'is the radical of at least one z-valent alcohol or phenol, this radical is linked by alcohol atom (s) or phenol-Lcos' to the P atom (s); R-'j. / R, 2 and R, 3 each independently of the others represents alkyl containing 1 to 30 carbon atoms; alkyl containing 1 to 18 carbon atoms, which is substituted by halogen, -C004 ', -CN or -CONR4'R4'; alkyl containing 2 to 18 carbon atoms, which is interrupted by -S-, -O- or -NR'4-; phenyl-alkyl with 1 to 4 carbon atoms; cycloalkyl containing 5 to 12 carbon atoms; phenyl or naphtyl; phenyl or naphthyl, each of which is substituted by halogen, 1 to 3 acyl radicals or alkoxy radicals containing a total of 1 to 18 carbon atoms or by phenyl-alkyl with 1 to 4 carbon atoms; or a radical of the formula where m is an integer in the range of 3 to 6; -R'4, or the radicals R4 ', each independently of the others are hydrogen; alkyl containing 1 to 18 carbon atoms; cycloalkyl containing 5 to 12 carbon atoms; or phenylalkyl containing 1 to 4 carbon atoms in the alkyl portion; R's and R'e each independently of the other is hydrogen; alkyl containing 1 to 8 carbon atoms, or cycloalkyl containing 5 or 6 carbon atoms; R'7 and R'8, wherein q = 2, each independently of the other is alkyl with 1 to 4 carbon atoms or together are a 2, 3-dehydropentamethylene radical; and R'7 and R'8, where q = 3, are methyl; the substituents R'14 each independently of the other are hydrogen; alkyl containing 1 to 9 carbon atoms or cyclohexyl; the substituents R '15 each independently of the other is hydrogen or methyl; and R'16 is hydrogen or alkyl having 1 to 4 carbon atoms, and in the case where several R'16 radicals are present, the R'16 radicals are identical or different; X 'and Y' each is a direct link or -O-; and Z 'is a direct link; -CH2 ~; -C (R'116) 2- or -S-. A particularly preferred process is that wherein the phosphite or phsphonite is that of the formula (1), (2), (5) or J 6), where n 'is the number 2, and y is the number 1 or 2; A 'is alkylene containing 2 to 18 carbon atoms; p-phenylene or p-biphenylene; E ', where y = l, is alkyl with 1 to 18 carbon atoms, -OR! or fluoro j and where y = 2, is p-biphenylene; R X, R'2 and R'3 each independently of the other is alkyl containing 1 to 18 carbon atoms; phenyl-alkyl with 1 to 4 carbon atoms; cyclohexyl; phenyl; phenyl which is substituted by 1 to 3 alkyl radicals containing a total of 1 to 18 carbon atoms; the substituents R'14 each independently of the other are hydrogen or alkyl containing 1 to 9 carbon atoms; R'is is hydrogen or methyl; X 'is a direct link; Y 'is -0-; and Z 'is a direct link or -CH (R'16) -. Of particular technical interest are those phosphites or phosphonites which are next in the list of possible co-stabilizers under item 4. In the novel process, preferably those benzofuran-2 -ones corresponding to formula (8) are employed. (8), wherein if n is 1, R: is naphthyl, phenanthryl, anthryl, 5,6,7, 8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo [b] thienyl, naphtho [2, 3-b] thienyl, thiantrenyl, dibenzofuryl, chromenyl, xanthenyl, phenoxyntinyl, pyrrolyl, imidazipyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, "indazolyl, purinyl, quinolizinyl , isoquinolyl, quinolyl, phthalazinyl, naphidinyl, quinoxalinyl, quinazolinyl, cinolinyl, pteridinyl, carbazolyl, beta-carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, fluorenyl or phenoxazinyl , each that is unsubstituted or - substituted by alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, hydroxy, halogen, amino, alkylamine with 1 to 4 carbon atoms, phenylamino or di (alkyl with 1 to 4 carbon atoms) carbon) amino, or Rx is a radical of the formula 9 (9) and if n is 2, Rx is phenylene or naphthylene unsubstituted or substituted with alkyl having 1 to 4 carbon atoms or hydroxy; or -R12-X-R13-, R2, R3, R4"and R5 each independently of the other is hydrogen, chloro, hydroxy, alkyl with 1 to 25 carbon atoms, phenylalkyl with 7 to 9 carbon atoms, unsubstituted phenyl or substituted with alkyl having 1 to 4 carbon atoms, cycloalkyl with 5 to 8 carbon atoms substituted with alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 18 carbon atoms, alkylthio with 1 to 18 carbon atoms, alkylamino with 1 to 4 carbon atoms, di (C 1-4 alkyl) amino, C 1 -C 25 alkanoyloxy, C 1 -C 25 alkanoylamino, C 3 -25 alkenyloxy; alkanoyloxy with 3 to 25 carbon atoms which is interrupted by oxygen, sulfur or? N-R14; cycloalkylcarbonyloxy with 6 to 9 carbon atoms, benzoyloxy or benzoyloxy substituted with alkyl having 1 to 12 carbon atoms; or R2 and R3, or R1 and R4, or R4 and R5, together with the linking carbon atoms are a benzene ring, R4 is additionally - (CH2) p-C015 or - (CH2) qOH or if R3, R5 and R6 are hydrogen, R4 is additionally a radical of the formula where Ra is as defined above for n = 1, Rb is hydrogen or a radical of formula 11 where R4 is not a radical of formula 10 and R? is as defined above for n = 1, R7, R8, Rg, Rio and Ru each independently of the other is hydrogen, "halogen, hydroxy, alkyl having 1 to 25 carbon atoms, alkyl having 2 to 25 carbon atoms which is interrupted by oxygen, sulfur or \ N R14, alkoxy with 1 to 25 carbon atoms, alkoxy with 2 to 25 carbon atoms which is interrupted by oxygen, sulfur or NR14; * '' 'at 25"carbon atoms, alkenyl with 3 to 25 carbon atoms, alkynylkoxy with 3 to 25 carbon atoms, alkynyl with 3 to 25 carbon atoms, alkynyloxy with 3 to 25 carbon atoms, phenylalkyl with 7 to 9 carbon atoms, phenylalkoxy with 7 to 9 carbon atoms, phenyl unsubstituted or substituted by alkyl with 1 to 4 carbon atoms, phenoxy unsubstituted or substituted by alkyl with 1 to 4 carbon atoms; cycloalkyl with 5 to 8 carbon atoms unsubstituted or substituted by 1 to 4 carbon atoms, cycloalkoxy with 5 to 8 carbon atoms unsubstituted or substituted by 1 to 4 carbon atoms, alkylamino of 1 to 4 carbon atoms , di (C 1 -C 4 alkyl) amino, C 1 -C 25 alkanoyl, C 3 -C 25 alkanoyl which is interrupted by oxígenoOxy, sulfur or N RR14; alkanoyloxy with 1 α / 25 atoms of carbon; alkanoyloxy with 3 to 25 carbon atoms that is interrupted by oxygen, sulfur or \ N - R14; alkanoylamino with 1 to 25 carbon atoms, alkenoyl with 3 to 25 carbon atoms; alkenoyl with 3 * to 25 carbon atoms which is interrupted by oxygen, sulfur or * '' 'N-R14; alkenoyloxy with 3 to 25 atoms / carbon ^ alkanoyloxy with 3 to 25 carbon atoms which is interrupted by oxygen, sulfur or \ NR14; cycloalkylcarbonyl with 6 to 9 atoms (carbon, cycloalkylcarbonyloxy with 6 to 9 carbon atoms, benzoyl or benzoyl substituted with alkyl with 1 to 12 carbon atoms, benzoyloxy or benzoyloxy substituted with alkyl with 1 to 12 carbon atoms; Rie O • * l «- O - C -JC - R15 or 'l -, R19 O c o R 2.3 H R22 or also in the formula 9, R7 and R8, or R8 and RX1 / together with the carbon atoms of bond, are a ring of benzene, VR? -2 and R -? - 3 each independently of the other are phenylene or naphthylene unsubstituted or substituted with alkyl having 1 to 4 carbon atoms, R14 is hydrogen or alkyl having 1 to 8 carbon atoms, R15 is hydroxy, R, alkoxy with 1 to 18 carbon atoms or N R16 and R17 each independently of the other are hydrogen, CF3, alkyl with 1 to 12 carbon atoms or phenyl, or Rlb and R17 together with the linking carbon atom are a cycloalkylidene ring with 5 to 8 carbon atoms which it is unsubstituted or substituted by 1 to 3 of alkyl with 1 to 4 carbon atoms; R-iß and Ri 9 each independently of the other are hydrogen, alkyl with 1 to 4 carbon atoms or phenyl, R20 is hydrogen or alkyl with 1 to 4 carbon atoms; R21 is hydrogen, phenyl unsubstituted or substituted with alkyl having 1 to 4 carbon atoms; alkyl with 1 to 25 carbon atoms; alkyl having 2 to 25 carbon atoms which is interrupted by oxygen, sulfur or N-R14; / phenylalkyl with 7 to 9 carbon atoms which is unsubstituted or substituted on the phenyl radical by 1 to 3 alkyl having 1 to 4 carbon atoms; phenylalkyl with 7 to 25 carbon atoms which is interrupted by oxygen, sulfur or NR14; / _ which is unsubstituted or substituted on the phenyl radical by 1 to 3 of alkyl having 1 to 4 carbon atoms, or R20 and R21, together with the linking carbon atoms, is a cycloalkylene ring with 5 to 12 carbon atoms. carbon that is unsubstituted or substituted by 1 to 3 of alkyl with 1 to 4 carbon atoms; R22 is hydrogen or alkyl with 1 to 4 carbon atoms, R23 is hydrogen, alkanoyl with 1 to 25 carbon atoms, alkenoyl with 3 to 25 carbon atoms; alkanoyl having 3 to 25 carbon atoms which is interrupted by oxygen, sulfur or? N-R14; alkanoyl with 2 to 25 atoms / carbon which is substituted by a di (alkyl with 1 to 6 carbon atoms) phosphonate group; C 6 -C 9 -cycloalkylcarbonyl, tenoyl, furoyl, benzoyl or benzoyl substituted with alkyl having 1 to 12 carbon atoms; 2 and 25 each independently of the other is hydrogen or alkyl having 1 to 18 carbon atoms, R26 is hydrogen or alkyl having 1 to 18 carbon atoms, R27 is a direct bond, alkylene with 1 to 18 carbon atoms; alkylene with 2 to 18 carbon atoms which is interrupted by oxygen, sulfur or? N-R14; alkenylene with 2 to 18 carbon atoms, / alkylidene with 2 to 20 carbon atoms, phenylalkylidene with 7 to 20 carbon atoms, cycloalkenylene with 5 to 8 carbon atoms, bicycloalkylene with 7 to 8 carbon atoms, phenylene unsubstituted or substituted by alkyl with 1 to 4 carbon atoms carbon.

R28 is hydroxy, [_0-_LMr +]. alkoxy with 1 to 18 carbon atoms or Ras OR R29 is oxygen, -NH- or N-C NH R, / R30 is alkyl with 1 to 18 carbon atoms or phenyl, R31 is hydrogen or alkyl having 1 to 18 carbon atoms, M is a r-valent metal cation, X is a direct bond, oxygen, sulfur or -NR31-, n is 1 or 2, p is 0, 1 or 2 , q is 1, 2, 3, 4, 5 or 6, r is 1, 2 or 3, and s is 0.1 or 2. Benzofuran-2 -ones of particular technical interest, are those listed below in the In addition, this invention relates to a composition, which comprises a) pentaerythritol-tetrakis (3- [3 ', 5' -di-tert-butyl-4 '-hydroxyphenyl] propionate ), and b) at least one compound of the benzofuran-2 -one type. The novel compositions containing pentaerythritol-tetrakis (3- [3 ', 5' -di-tert-butyl-4 '-hydroxyphenyl] propionate) (component a) preferably in amorphous form. Particularly preferred compositions are those comprising the components a and b side by side, in the same amorphous phase. The stabilizer compositions of the invention usually contain less than 10% by weight of polymeric or high molecular weight components, typically those having a weight molecular weight of 1500 g / mol or more; Primarily no such high molecular weight components are present. Use as stabilizer for organic material The products of the process of this invention, the novel amorphous compounds, the stabilized color compound 13, according to this invention and also the novel β-crystalline modification of the compound 14 are particularly suitable for stabilizing organic materials, against damage by light, oxygen or heat. The materials to be stabilized can for example be oils, greases, paint systems, cosmetics, photographic materials, or biocides. Of particular interest is the use in polymeric materials as in the case of plastics, rubber, coating materials, photographic material or sizing. When used in cosmetic preparations, the material to be protected is often not the preparation itself, but the skin or hair to which the preparation is applied. Illustrative examples of polymers and other substrates that can be stabilized in this manner are: 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as polymers of cycloolefins, for example of cyclopentene or norbornene, polyethylene (which may optionally be interlaced) for example high density polyethylene (HDPE), high density polyethylene and high molecular weight (HDPE-HMW), high density and ultra high density polyethylene -high molecular weight (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and (ULDPE). Polyolefins, ie the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different methods and especially by the following: a) radical polymerization (usually with high pressure and at elevated temperature). b) catalytic polymerization using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic table. These metals usually have one or more of a ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyl, alkenyls, and / or aryls that can already be coordinated p or d. These metal complexes can be in the free form or fixed in substrates, typically in activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts can be soluble or insoluble in the medium of "polymerization. The catalysts may themselves be used in the polymerization or additional activators may be employed, typically metal alkyls, metal hydrides, metal alkylhalides, metal alkyl oxides, or metal alkyloxanes, metals are elements of the groups, lia and / or Illa of the Periodic Table. The activators can be conveniently modified with additional ester, ether, amine or silyl ether groups. These catalyst systems are usually referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC). 2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (for example LDPE / HDPE). 3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene / propylene copolymers, linear polyethylene of , low density (LLDPE) and its mixtures with low density polyethylene (LDPE), propylene / but-1-ene copolymers, propylene / isobutylene copolymers, ethylene / but-l-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, pr opium 1 / bu tad no copolymers, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, copolymers of ethylene / vinyl acetate, and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene norbornene; and blends of these copolymers with each other and with polymers mentioned in 1) for example polypropylene / ethylene / propylene copolymers, copolymers of LDPE / ethylene vinyl acetate (EVA), LDPE / ethylene acrylic acid (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random carbon monoxide / polyalkylene copolymers and their mixtures with other polymers, for example polyamides. 4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof (for example tackifying agents) and mixtures of polyalkylenes and starch. 5. Polystyrene, poly (p-methylstyrene), poly (methylstyrene). 6. 'Copolymers of styrene or o-methylstyrene with f-dienes or acrylic derivatives, for example styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methaclate /, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; mixtures of high impact strength ote styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene / propylene / diene terpolymer; and styrene block copolymers such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / non-butylene / styrene or U is irene / ethylene / propylene / is irene. i '7. Styrene or α-methylstyrene graft copolymers, for example styrene in polybutadiene, styrene in polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) in polybutadiene; styrene, acrylonitrile and methyl methacrylate in polybutadiene; styrene and maleic anhydride in polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide in polybutadiene; styrene and maleimide in polybutadiene; styrene and alkyl acrylates or methacrylates in polybutadiene; styrene and acrylonitrile in ethylene / propylene / diene terpolymers; styrene and acrylonitrile in polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile in acrylate / butadiene copolymers, as well as their mixtures with the copolymers listed under 6), for example mixtures of copolymers known as ABS, MBS, ASA or AES polymers. 8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, homo- and epichlorohydrin copolymers, especially polymers of compounds of vinyl containing halogen, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as their copolymers such as yinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or copper chloride copolymers vinylidene / vinyl acetate. 9. Polymers derived from acids, β-unsaturates and their derivatives such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles. modified by impact with butyl acrylate. ID. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example copolymers of acrylonitrile / butadiene, copolymers of acrylonitrile alkyl acrylate, copolymers of acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide or terpolymers of acrylonitrile / alkyl methacrylate / butadiene. 11. Polymers derived from unsaturated alcohols and amines or the acrylic derivatives or their acetals, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above. 12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or their copolymers with bisglycidyl ethers. ? 13. Polyacetals such as polyoxymethylene and those polyoxymethylenes containing ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS. 14. - Polyphenylene oxides and sulphides and mixtures of polyphenylene oxides with styrene polymers or polyamides. 15. Polyurethanes derived from polyethers, polyesters or polybutadienes terminated with hydroxyl on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as their precursors. 16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6 , 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or / and terephthalic acid and with or without an elastomer as a modifier, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems). 17. Polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles. 18. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolciumhexan terephthalate and polyhydroxybenzoates, as well as copolyether block esters derived from polyethers terminated with hydroxyl; and also polyesters modified with polycarbonates or MBS. 19. Polycarbonates and polyester carbonates. 20. Polysulfones, polyether sulfones and polyether ketones. 21. Interlaced polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other side, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins. 22. Alkyd resins drying and not drying. 23. Unsaturated polyester resins derived from copolyesters of dicarboxylic acids, saturated and unsaturated with polyhydric alcohols and vinyl compounds as entanglement agents and also their halogen-containing modifications of low flammability. 24. Interlaxable acrylic resins derived from substituted arylates, for example epoxy acrylates, urethane acrylates or acrylate polyesters. a -, 25 Alkyd resins, polyester resins and acrylate resins, entangled with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins. 26. Interlaced epoxy resins which are derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example products of diglycidyl ethers of bisphenol A and bisphenol F, which are entangled with customary hardeners such as r-1. J anhydrides or amines with or without accelerators 27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or cellulose ethers such as methyl cellulose; as well as turpentine resins and their derivatives. 28. Mixtures of the aforementioned polymers (poly-blends), for example PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / PE, PVC / acrylates, POM / PUR thermoplastic, PC / PUR thermoplastic, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6. 6 and copolymers, PA / HDPE, * PA / PP, PA / PPO, PBT / P / ABS OR PBT / PET / P. This invention therefore also relates to a composition comprising: A) an organic material susceptible to oxidative, thermal or / and actinic degradation and, and B) the amorphous form of one of the compounds No. 1-12, , 18, the amorphous compound stabilized in color 13 and / or the β-crystalline form of compound 14 as a stabilizer, as well as to the use of the amorphous form of one of compounds Nos. 1-12, 14, 18, of the amorphous compound stabilized in color 13 and / or of the ß-crystalline form of compound 14 for 7 'stabilize material organic against degradation or oxidative, thermal or actinic accumulation. Component B is preferably the amorphous form for one of compounds Nos. 1-12, 14, 18 and also the β-cristamine form of compound 14.The invention also relates to a process for stabilizing organic material against thermal, oxidative or / and actinic degradation or accumulation, which comprises applying the amorphous form of one of compounds Nos. 1-12, 14, 18, the amorphous compound is stabilized in color 13 and / or the ß-crystalline form of the compound "14, to this material and / or preferably adding it as well as to its corresponding use." The amorphous form of one rt of the compounds Nos. 1-12, 14, 18, the amorphous compound stabilized in color 13 and / or the β-crystalline form to compound 14 can be used here by themselves or as a component of a mixture of the amorphous form of one or more compounds Nos. 1-12, 14, 18 , of the amorphous compound stabilized in color 13 and / or the crystalline form of compound 14 with the conventional crystalline form and / or other conventional additives.The amount of the stabilizer (amorphous and if crystalline is required) to be used in total, depends on the organic material to this and the intended use of the stabilized material. The novel composition generally comprises 100 parts by weight of component A, 0.01 to 15, preferably 0.05 to 10 and more preferably 0.1 to 5 parts by weight of the novel stabilizer (novel amorphous modification of one of compounds Nos. 1-12). , 14, 18, amorphous compound stabilized in color 13 and / or the ß-crystalline form of compound 14 or mixture comprising an amorphous or novel ß-crystalline modification.It is particularly interesting to use the novel stabilizer in synthetic organic polymers as well as compositions corresponding, in particular thermoplastic polymers which are processed at elevated temperatures, for example by extrusion, blow molding, calendering, injection molding, casting, compression, sintering, spinning, foaming, welding, rolling, thermoforming, and the like. The organic materials to be protected are preferably natural semi-synthetic or synthetic organic materials. The bear can be used particularly advantageously in compositions comprising as component A, a synthetic organic polymer, preferably a thermoplastic polymer or a binder for coatings such as paint systems. Suitable thermoplastic polymers are, for example, polyolefins, preferably polyethylene (PE) and polypropylene (PP) lm as well as those polymers containing hetere atoms in the main chain In a preferred aspect, this invention also relates to a pomposition wherein the The novel modification is incorporated in a thermoplastic polymer, in a paint binder, in particular one based on an acrylic resin, alkyd, polyurethane, polyester or polyamide or corresponding modified resins or in a photographic material .The material to be protected (component A) in this case may be a thermoplastic polymer, a paint binder, in particular based on an acrylic resin, alkyd, polyurethane, polyester or polyamide or corresponding modified resins, a photographic material or a dye present in this material. of the novel modifications like stabilizers pair to coatings, for example for painting systems. The incorporation in the materials to be stabilized for example, can be carried out when mixing or applying the novel stabilizer and if other additives are required, by the usual methods of the technique, in the case of polymers, in particular of synthetic polymers, the incorporation it can be carried out before or after molding, or by applying the dissolved or dispersed compound to the polymer, if required with subsequent evaporation of the solvent. Elastomers such as latexes can also be stabilized, another possibility of incorporating the novel stabilizer into polymers consists in their addition before, during or immediately after the polymerization of the corresponding monomers or before entanglement. The amorphous or ß-crystalline compound in this case can be added as such or also in encapsulated form (for example in waxes, oils or polymers). If the stabilizer ^ is added before or during polymerization, it can also serve as a chain length regulator (chain terminator) for the polymers.

The novel stabilizer can also be added to the plastics to be stabilized in the form of a masterbatch comprising the stabilizer, for example in a concentration of 2.5 to 25% by weight. The incorporation of the novel stabilizer can conveniently be carried out by the following methods: as dispersion p emulsion (for example for latices or emulsion polymers), - as a dry mixture before adding the additive components or polymer blends, by direct addition to the apparatus of processing (for example extruder, internal mixer, etc.), as a solution or fusion. The novel stabilizer is preferably added to the polymer before or after processing, preferably as a "dry mix" during the mixing of the additive components or polymer blends, or by direct addition to the processing apparatus. this invention can be used in different forms or can be processed to different products, for example metal foils, fibers, filaments, molding compositions, profiles or binders for paint systems, primers or masillas- both the novel stabilizer compositions novel ^ they may comprise as additional component (C) one or more conventional additives, such as antioxidants and additional light stabilizers, metal deactivators, phosphites or phosphonites, Illustrative examples thereof are: 1. Antioxidants 1- ^ 1, Alkylated monophenols, for example 2, 6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethyl lfenol, 2, 6-di-tert-butyl-4-n-butylphenol, 2, 6-di-tert-butyl-4-isobutiIfenol, 2, 6-dicyclopentyl-4-methylphenol, 2- (alpha-methylcyclohexyl) - 4, 6 -dimetilfenol, 2, 6-dioctadecyl-4-methylphenol, 2, 4, 6-tricyclohexylphenol, 2, 6-di-tertbutyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example 2 , 6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1 '-methylundec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) ) phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) phenol and mixtures thereof. 1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2, 4-dioctylthiomethyl-6-methylphenol, 2, 4-dioctylthiomethyl-6-ethylphenol, 2, 6-di -dodeciltiometil -4 -nonilfenol. 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 α-tocopherol, β-tocopherol, α-tocopherol, d-tocopherol and their mixtures (Vitamin E). 1.5. Hydroxylated thiodiphenyl ethers. for example 2,2'-t-iobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol) , 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis- (3,6-di-sec-amylphenol), 4,4'-bis (2,6-dimethyl) -4-hydroxyphenyl) disulfide. 1. 6. Alquili_denbisfenoles. for example 2, 2 '-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-eethyl enb is [4-methyl] -6- (alpha-methylcyclohexyl) phenol], 2, 2 '-met ilenbis (4-methyl-6-cyclohexylphenol), "2,2'-methylenebis (6-nonyl-4-methylphenol), 2' -methi lenbis (4,6-di-tert-butyl-enol), 2,2'-ethylidebisbis (4 ^ .6-di-tert-butylphenol), 2,2'-ethylidebis (6-tert-butyl-4) isobutylphenol), 2,2'-methylenebis [6- (-methylbenzyl) -4 -nonylphenol], 2,2'-methylenebis [6- (a, a-dimethylbenzyl) -4-nonylphenol], 4, 4 '- methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-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) ) Utane, 1, 1-bis (5-tert-butyl-4-hydroxy- - "« L - .bb 2-methyl-phenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methyl-phenyl) dicyclopentadiene, bis [2- (3 '-tert-butyl-2' -hydroxy-5 '-methylbenzyl) -6-tert-butyl-4-methylfenyl] terephthalate, 1, 1-bi s - (3, 5-dimet i 1 - 2-hydroxyphenyl) butane, 2,2-bis- (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n- dodecylmercaptobutane, 1, 1, 5, 5- tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane. 1..7. 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, tridecyl-4-hydroxy-3, 5-dihydroxy-3-hydroxy-3,5-dihydroxydibenzyl ether. tert-butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di) -tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate. 1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis- (3,5-di-tert-butyl-2-hydroxybenzyl) -malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5- methenylbenzyl) -malonate, didodecylmercaptoethyl-2, 2-bis- (3, 5-di-tert-butyl- "4-hydroxybenzyl) malonate, bis [4- (1,1, 3,3-tetramet i 1 useful ) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate. 1. 9. Hydroxybenzyl aromatic 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. Compounds' triazine, for example 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3, 5-di-tert-butyl-4-T idroxianilino) -1,3,5-triazine, 2-octylmercapto -4,6-bis (3,5-di-tert-butyl-4-hydroxy-enoxi) -1 , 3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxy-enoxy) -1,2,3-triazine, 1,3,5-tris- (3,5-di-butyl) -4-hydroxybenzyl) isocyanurate, 1,3, 5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-ter) -butyl-4- hydroxy-phenylethyl) -1, 3, 5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxy-phenylpropionyl) -hexahydro-1,3,5-triazine , 1,3, 5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate. 1.11. Benzyl phosphates, 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-methylbenzylphosphonate, the calcium salt of the monomethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid. 1. 12. Acylaminophenols, for example 4-hydroxylauranylide, 4-hydroxysteatenylidene, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate, to. 1.13 Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, for example methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol , 1, 9-nonandiol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol , 3-thiapentadecanol, trimethylhexandiol, trimethylpropane, 4-hydroxymethyl-l-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane. 1.14. Esters of β- (5-tert-butyl-4-hydroxy-3-methyl-phenyl) propionic acid with mono- or polyhydric alcohols, for example with, methanol, ethanol, n-octanol, i-octanol, octadecanol, 1, 6 -hexandiol, 1, 9-nonandiol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-, 6, 7-trioxabicyclo [2.2.2] octane. 1.15, Esters, of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonahdiol, ethylene glycol, 1,2-propanediol, neopentyl glycol, tipdiethylene glycol, diethylene glycol, tri-ethyl in glycol, pent aeritriol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexandiol, trimethylolpropane, 4-hydroxymethyl-1-phosph -2,6,7-trioxabicyclo- [2.2.2] octane. 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alcohols for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, , 2-propanediol, neopentyl glycol, tiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4 -hydroxymethyl-l-phospha-2, 6, 7-trioxalSyclo [2.2.2] octane. 1.17. Amide - ß- (3, 5-di-tert-butyl-4-hydroxyphenylH) ropionic acid, for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) - hexamethylenediamide, N, N'-bis (3, 5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazide, N, N'-bis [2- (3 - "['3, 5 -'-di-tert-butyl-4-hydroxy-enyl] -propionyloxy) -ethyl] -oxamide (Naugard ™ XL-1 supplied by Uniroyal) 1.18 Ascorbic acid (vitamin C) 1.19.Amino antioxidants, for example N, N'-di-isopropyl-p-phenylenediamine, N, N '-di-sec -but il -p- • phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p -f enylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -pf-enylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, '-dicyclohexyl-pf-enylenediamine, N,' -difenyl-p-phenylenediamine, N, N'-bis (2-naphyl) -pf enylenediamine, N-isopropyl-N '-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) - N' - phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylene diamine, 4- (p-toluenesulfamyl) diphenylamine, N, N'-dimethyl -N, N '-di -sec-butyl-pf enilendiamine, diphenylamine, N-allyldifenylamine, 4 - . 4-isopropoxy-diphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, '-di-ter- O-1-diphenylamine, 4-n-buty-1-aminofenol, 4-but-irylaminofenol, 4-nonanoylaminophenol, 4-dodecanoylamino-phenol, 4-octadecanoylamino-enol, bis (4-methoxy-phenyl) -amine, 2,6- di-te * r -butyl-4-dimethylaminomethylphenol, 2,4'-diaminodifenylmethane, 4,4'-diaminodifenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodifenylmethane, , 2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, N - tert-octylated phenyl-1-naphthylamine, a mixture of dialkylated mono-tert-butyl / tert-octyl-diphenylamines, a mixture of mono- and dialkylated nonyl diphenylamines, a mixture of mono- and dialkylated dodecyldifenylamines, a mixture of mono- and dialkylated isopros- pyl / isohexyldiphenylamines , a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro- 3, 3-dimethyl-4H-l, 4-benzothiazine, phenothiazine, a mixture of tert-butyl / tert-octylphenothiazines mono- and dialkylated, a mixture of mono- and dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N, N, N ', N' -tetraphenyl-1,4-diaminobut-2-ene, N ^ N-bis (2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine, bis (2, 2, 6,6-tetramethylpiperid-4-yl) sebacate, 2, 2, 6, 6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol. 2. Absorb --- e --- ^ of U? Z ~ v e -.stabilizers of light 2.1. 2 - ('-Hydroxyphenyl) benzotriazoles, for example 2- (2'-hydrox-x, i-5'-methylphenyl) benzotriazole, 2- (3', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxy-phenyl) -benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3') , 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) 5-chloro-benzotriazole, 2- (3 '-sec-butyl-5' -tert-butyl-2 '-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4-r -octylp-xyphenyl) benzotriazole, 2- (3', 5'-di-ter) -amil-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis- (, -dimethylbenzyl) -2'-hydroxyphenyl) -benzotriazole, 2- (3'-tert-butyl-2' - hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxy-phenyl ) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl- 2 '-hydroxy-5' - (2-methoxy-carbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3 '-ter-butyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxy phenyl) benzotriazole, 2- (3 '-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 '-ter-butyl-2' -hydroxy-5 '- (2-isooctyloxy-carbonylethyl) phenylbenzotriazole, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6- benzotriazol-2-ylphenol]; the transesterification product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO-CH2CH2] 2- where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2- [2'-hydroxy-3 '- (a, a-dimethylbenzyl) -5' - (1,1, 3,3-tetramethylbutyl) phenyl} benzotriazole; 2- [2'-Hydroxy-3 '- (1,1,3,3-tetramet-ilbutyl) -5' - (a, -dimethylbenzyl) phenyl} benzotriazole- 2.2- ^ 2 -Hydro-xi-benzophenones, for example the derivatives of 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4, 2 ', 4' -trihydroxy and 2 '-hydroxy-4,4'-dimethoxy. 2.3. Substituted and unsubstituted benzoic acid esters, for example 4-tert-butyl phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 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-hydrobenzoate, 2-methyl-4, 6-di-tert- '* * * butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate. 2.4. Acrylates, "for example ethyl oc-cyano-beta, beta-di-phenylacrylate, isooctyl O-cyano-beta ta, beta-diphenylacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-beta-methyl-p-methoxy-cinnamate, butyl a-cyano-beta-methyl-p-methoxy-cinnamate, methyl a-carbomethoxy-p-methoxycinnamate and N- (beta-carbomethoxy-beta-cuanovinyl) -2-methylindoline 2.5 Nickel compounds, eg complexes of 2-, 2'-thio-bis- [4- (1, 1, 3, 3-tetramethylbutyl) phenol] nickel, such as the 1: 1 or 1: 2 complexes, with or without additional ligands such as n-butylamine , triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, for example methyl or ethyl ester of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, for example of 2 - hydroxy-4-methylphenyl undecylketoxime, l-phenyl-4-lauroyl-5-hydroxypyrazole nickel complexes, with or without additional ligands, 2.6 Spherically hindered amines, r example bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate, bis (2, 2,6,6-tetramethyl-4-piperidyl) succinate, bis (1, 2, 2, 6, 6 pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1, 2, 2, 6, 6-pentamethyl-4-piperidyl) n- butyl -3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1- (2-hydroxyethyl) -2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N , N'-bis (2, 2, 6, 6-tetramet-il-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1, 3,5-triazine, tris (2,2,6 , 6-tetramethyl-4-piperidyl) nitrilotriácetato, tetraquis (2, 2, 6, 6-tetrametil-i 4-piperidil) -1,2,3, 4_-butan-tetracarboxilato, 1, 1 '- (1, 2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1, 2, 2, 6, 6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-oc til-7, 7,9, 9-tetramethyl-l, 3,8-triazaspiro [4.5] decan-2,4-dione, bis (l-octyloxy-2, 2,6,6-tetramethylpiperidyl) sebacate, bis ( l-octyloxy-2, 2,6,6-tetramethoxypiperidyl) succinate, * r linear or cyclic condensate of N, N'-bis- (2, 2, 6, 6-tetramethyl-4-piperidyl) hexamethylene diamine and 4-morpholin-2,6-dichloro- 1, 3, 5-triazine, the condensate of 2-chloro-4-6-bis (4-n-but-lamino-2, 2,6,6-tetramethyl-piperidyl) ) -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-pentamethyl piperidyl) -1,3,5-triazine and 1,2-bis- (3-aminopropylamino) ethane, 8 -acetyl-3 -dodecyl -7,7,9,9-tetramethyl-1 , 3, 8 -triazaspiro [4.5] -decan-2,4-dione, 3 -dodecyl-1- (2t, 2, 6, '6 -tetramet-il-4-piperidyl) pyrrole idin-2, 5-dione, 3-dodecyl-l- (1, 2, 2, 6, 6-pentamethyl-4-piperidi! Tpirrolidin-2y 5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2, 2, 6, 6 tetramethylpiperidine, a condensation product ion of N, '-bis (2, 2, 6, 6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of 1,2 -bis (3-aminopropylamino) -ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylamino-2, 2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N- (2, 2, 6, 6-tetramethyl-4-piperidyl) -n-dodecyl succinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dodecyl succinimide, 2 -undecyl -7, 7,9,9-tetramethyl-l-oxa-3, B-diaza-4-oxo-spiro [4, 5] decane, a reaction product of 7, 7, 9, 9-tetramethyl-2- cycloundecyl-l-oxa-3, 8-diaza-4-oxospiro [4, 5] decane and epichlorohydrin, 1, 1-bis (1,2,2,6,6-pentamethyl-4-piper id loxycarboni 1) -2- (4-methoxy phenyl) ethene, N, N '-bis-f ormyl-N, N' -bis (2, 2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, 4-methoxymethyl acid diester ? -malonic with 1, 2, 2, 6, 6-pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3 -oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, a product of anhydride-to-olefin maleic acid copolymer reaction with 2, 2, 6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine. 2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxyanilide, 2,2'-didodecyl-5, 5'-di- ter-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxyanilide and its mixture with 2-ethoxy-2 ' -ethyl-5,4'-di-tert-butoxyanilide, mixtures of oxanilides and p-methoxy disubstituted and mixtures of o- and p-ethoxy disubstituted oxanilides. 2.8. 2- (2-Hydroxyphenyl) -1,3,5-triazines, for example 2,4,6-tris (2-hydroxy-4-o-tyloxyphenyl) 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-propyl-oxyphenyl) -6- (2, -dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy) -4- octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3 , 5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2 - hydroxy-3-butyloxy-propoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triaxine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy- propyloxy) -phenyl] -4, * 6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxy-phenyl] -4 , 6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-Hydroxy-3-dodecyloxy-propoxy) phenyl] -4,6-bis (2 , 4-dimethyl f nil) -1, 3, 5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-d 4? -phenyl-1,3,5-triazine, 2- (2-hydroxy-4) -methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-l? idroxy-4 - (3-butoxy-2-hydroxy-propoxy) phenyl] -1, 3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-tr? A * z'm. a, 2- x [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'-diphenyloxamide, N-salicylal-N '-salicyloyl hydrazine, N, N'-bis (salicyloyl) hydra-zine, N, N'-bis (3,5-dihydro), tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzyl, ide;) Joxallyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N, N'-diacetylacG-poyl dihydrazide , N, N'-bis (salicyloyl) oxalyl dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide 4. Phosphites and Phosphonites, for example triphenyl phosphite, diphenyl * alkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, * distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol • diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, 'bis ( 2, 6-di-tert-butyl-4-methylphenyl) - pehtaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6- tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butyl-phenyl) -4,4'-biphenylene diphosphonium, 6-isooctyloxy-2, 4,8, 10-tetra-ter -butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphozin, 6-fluoro-2, 4, 8, 10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3, 2-dioxaphosphozin, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite , bis (2,4-di-tert-butyl-6-ethylphenyl). ethyl, 2, 2 ', 2"-nitrile [triethyltris (3, 3', 5, 5 '-tetra-tert-butyl-1,1' -biphenyl-2,2'-diyl) phosphite], 2- ethylhexyl (3, 3 ', 5, 5' -tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite The following phosphites are especially preferred: Tris (2,4-di- ter-butylphenyl) phosphite (IrgafosMR168, Ciba-Geigy), tris (nonylphenyl) phosphite, (G) . Sidroxylamines, 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-octadecylhydroxyl-amino, N-heptadecyl-N-octadecyl-hydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated tallow amine. 6. Nitrones, for example N-benzyl-a-phenyl-nitrona, N-ethyl-a-methyl-nitrona, N-octyl-a-heptyl-nitrona, N-lauryl-a-undecyl-nitronate, N-tetradecyl- a-tridecyl-nitrone, N-hexadecyl-a-pentadecyl-nitronate, N-octadecyl-a-heptadecyl-nitrone, N-hexadecyl-a-heptadecyl-nitrone, N-ochatadecyl-pentadecyl-nitronate, N-heptadecyl-oyl -heptadecyl -nitrona, N-octadecyl-hexadecyl-nitrone, nitrone derived from N, N-dialkylhydroxylamine derived from hydrogenated tallow amine. 7. Thiosineratists, for example dilauryl thiodipropionate or distearyl thiodipropionate. 8. Peroxide scavengers, for example esters of beta-thiopropionic acid, for example lauryl, stearyl, myristyl or tridecyl steres, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, dibutyldithiocarbamate zinc, dioctadecyl disulfide, pentaerythritol tetrakis (beta-dodecyl mercapto) -propionate. 9. Polyamide stabilizers, for example copper salts in combination with iodides and / or phosphorus compounds and divalent manganese 3-e salts. 10. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example stearate of calcium, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatechol or zinc pyrocatechol. 11. Nucleating agents, for example inorganic substances such as talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and their salts, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate, or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers). 12. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibers, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood sawdust and flours or fibers of other natural products, synthetic fibers. 13. Other additives, for example plasticizers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and blowing agents. 14. Benzofuranones and indolinones, for example those described in U.S. Pat. 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-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl -3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3 '-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] -phenyl) ben .zofuran-2 -one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) -benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7 - di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (3,4-dimethylphenyl) - 5,7-di-tert-butyl-benzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one. The type and quantity of additional stabilizers added are determined by the type of substrate to be stabilized and by its intended use; often 0.0005-10 is added, for example 0.001-5, preferably 0.01-2.5%, in weight, based on the material to be stabilized. It is particularly advantageous to use novel modifications of compounds Nos. 1, 10, 11 and / or 14 in combination with sterically hindered amines, for example 2, 2, 6, 6-tetralkylpiperidine derivatives. This invention therefore relates to a synergistic stabilizing mixture, comprising (a) the beta-crystalline modification of compound 14 and / or the amorphous modification of compounds Nos. 1, 10, 11 and / or 14, and (b) at least one sterically hindered amine, its salt with any acid or its complex with a metal, as well as a composition, comprising A) an organic material susceptible to oxidative, thermal or / and actinic accumulation, B) beta-modification Crystalline of compound 14 and / or the amorphous modification of compounds Nos. 1, 10, 11 and / or 14, and also C) a conventional additive of the sterically hindered amine type. Preferred sterically hindered amines, for example, are those given in the above list under item 2.6. It is also particularly advantageous to use the novel modifications in combination with co-stabilizers of the type 2- (2-hydroxyphenyl) -1, 3, 5-triazine, as exemplified in the above list under item 2.8. The invention is illustrated by the following Examples. In the Examples, as well as in the remaining description and in the patent claims, all parts or percentages are given by weight, unless otherwise stated. The temperatures are determined by differential thermoanalysis [DSC], at a heating rate of 4 ° C / min (p.f.) or 20 ° C / minute (TG), unless stated otherwise. In the Examples, compound A is bis (2, 2,6,6-tetramethylpiperidin-4-yl) sebacate. In the Examples, compound B is a commercially available mixture of different phosphonites (CAS-No 119345-01-6) having the main components (ca. p °, c) The following abbreviations are used in the Examples and Tables: DSC: differential scanning calorimetry (quantitative dynamic differential thermoanalysis) Tg or TG - glass transition temperature (DSC, + 20 ° C / min) h, min: hour (s), minute (s) pf melting point (DSC, + 4 ° C / min) Example 1: Preparation of the amorphous form --- of the compound No. the laboratory scale A boiling flask with a capacity of 30 ml, is charged with 10 g of 2, 2'-methylenebis (pulverulent crystalline crystalline 4- (1, 1, 3, 3-tetramethylbutyl] -6-benzotriazol-2-yl-phenol) (compound No. 1) which is heated under nitrogen indirectly by bucket sieve and burst Controllable heat (air temperature 235-245 ° C). At 200 ° C, the powder becomes a pale yellow, transparent, low viscosity melt, which is tempered at 205 ° C. After pouring the melt into portions on a stainless steel plate cooled to 15 ° C with water, the melt rapidly becomes highly viscous and solidifies spontaneously. Nodules are prepared from part of the melt by dripping on the cooled steel plate. The vitreous composition can be easily separated from the cooling plate and pulverized in a mortar. DSC (Heating rate 20 ° C / minute) confirms the amorphous structure Tg = 72-75 ° C. Example: Preparation of the amorphous form of compounds 1-12, 18, 19 on a laboratory scale As described in Example 1, a boiling flask with a capacity of 30 ml is charged with 10 g each of a powdery compound crystalline that is heated under nitrogen indirectly by ladle sieve and heat blast controllable. A T > melting point (p.f-), the powder becomes a colorless, light-colored, clear, low-viscosity melt that is quenched to Ti. After pouring the melt into portions in a stainless steel plate cooled to Tw with water, the melt quickly becomes highly viscous and solidifies spontaneously. Nodules form part of the melt when dripping on the cooled steel plate. The vitreous composition can be easily separated from the cooling plate and if desired can be sprayed at T < Tg in a mortar. The following table gives molecular weight, melting point (m.p.) of the crystalline form and the glass transition temperature (Tg; jump-Cp according to DSC) of the amorphous form: No. molecular weight p. f. Ti TW T9 • g / mol ° _C ° _C ° C ° C (+ 20 ° C / min) 1) 658 197 205 15 73-74 2) 358 161 185 15 30-31 3) 594. .8 177 190 15 59-60 4) 636. .9 160 185 15 54-55 ) 775 Í79; 243 250 15 97-98 6) 784 220 225 15 109-110 7) 553 200; 221 225 15 69-70 8) 699 158 170 15 115-120 9) 685 148 165 15 44-45 ) 447. .6 139 160 10 41-42 11) 323. .4 154 170 5 19-20 12) 350. .5 132 145 10 24-25 18) 552 163 170 10 52-55 19) 441. .4 113 120 15 33-34 The novel amorphous modifications of the above compounds give an X-ray diffraction pattern and free of lines with Cu-K radiation - The novel amorphous form is solid below TG and plastic on TG. Typical data for the viscosity of the plastic amorphous form at 130 ° C and the known melting of the compound (1) (liquid state, 200 ° C) at different shear rates D are found in the following Table; the data has been determined using a Rotary viscometer type 30 / Rheotemp, cone and plate measuring system. Tab. : Viscosity (Pas) of the compound (1) in the plastic state (130 ° C) and in the liquid state (200 ° C) D = ls "D = 3 s" D = 60 s "plastic 40 40 20 liquid 0.4 0.13 Example 2: Preparation of amorphous nodules The melting of compound No. 1 is dripped at 200-205 ° C and a yield of 20 kg / h by a device of the SANDVIK-Rotoformer ™ type (feed width 0.25 m) and is pelleted in a cooling conveyor with length of 4.5 m, tempered at 15-25 ° C with water.The required cooling time is varied in the range of 8 s to 60 s by the speed of the conveyor; The droplet diameter is 1 mm (8 s of cooling time) to 4 mm (60 s of cooling time). Amorphous nodules are obtained having the properties described in Example 1. Example 2a: A fusion of one of the compounds 2, 3, 4, 5, 6, 7, 8, 9, 18 or 19 each is processed by the method described in Example 2. Amorphous nodules are obtained with the properties described in Example la. Example 3: Use of compound (1) in the novel extrusion process --- 2,2'-Methylenebis (4- [1,1,3, 3-tetramethylbutyl] -6-benzotriazol-2-yl-phenol) it adds gravimetrically in pulverulent form to a yield of 19 kg / h in a twin screw extruder in the laboratory (Bühler, Type DNDL 44). The diameter of the spindle is 44 mm, the length / diameter ratio (L / D) is 40 to 10 barrels, rotational speed of the spindle 130 min-1. The laboratory extruder is heated as follows: barrel 1 (powder addition): cooling water (15 ° C), barrels 2/3/4: oil at 205 ° C, barrels 5/6/7: oil at 210 ° C, barrels 8/9/10: hydraulic water at 120 ° C. Under these conditions, the powder is melted at about 70% up to barrel 7. The initially low viscosity paste is rapidly cooled to 130 ° C from barrel 8 onwards (sub-cooled melting component approximately 30%). At a dynamic pressure of 11 bar, threads that can be cut are obtained after the heated die plate (223 ° C, 2 free holes of 2.5 mm each). Hot cutting by a rotating blade at a cutoff frequency of 123 s "1, gives soft granules that are subcooled in a fluidized bed cooler with subsequent air crystallization The following properties are found: particle size (dimension minimum-maximum): 2 - 5 mm volumetric density: 510 - 590 Kg / 1 resting angle (DIN- ISO norm 4324) 40 ° flow time (DIN norm 53492): 2.7 s (F = 25 mm) evolution-- of powder Test Heubach): <0.1 G% after 5 min crystallinity (DSC): about 95-99% Example 4: Stabilization of polycarbonate (PC) 4985 G of polycarbonate powder (LexanMR145, producer: General Electric) is mixed with 15 g of novel stabilizer (product of Example 1, pulverulent) in a Henschel mixer at room temperature. The powder mixture thus obtained is processed into granules using an Extrusiometer Góttfert MP 2.3.0 at a temperature setting of 260/270/280/280 ° C at 60 rpm and at a pressure of 61.5 bar and a shear force of 47.3 Nm .

Plates with a thickness of 2 mm are produced from the granules thus obtained, by an injection molding process (matrix temperature 300 ° C, fusion temperature 120 ° C). The plates are exposed to light on an Atlas C165 Meter under the following conditions: black standard temperature 63 ° C, relative humidity 60% (dry phase), cycle 102 min. dry / 18 min. wet, irradiation 0.35 W / m2 at 340 nm. The discoloration of the samples is examined before the weathering begins, and then at regular intervals, when measuring the yellowness index (Yl, ASTM D 1925 method). The results are compiled in Table 1; Yl (O) indicates the initial color (= yellowing index before the weathering starts). Table 1: yellowing index Yl and embrittlement before and during weathering - weathering time / h stabilizer 0 500 950 1214 0.3 6.5 6.7 11.5 16.1 The novel stabilizer exhibits excellent effectiveness in the weathering test. Example 5: Preparation of solid phase single amorphous mixtures Mixtures of 2,2 '-methylenebis (4 - (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl-phenol) (compound 1) and tris (2,4-di-tert-butylphenyl) phosphite (mp 180-185 ° C) in a weight ratio of 10: 1 and 5: 1 are melted and cooled by the method described in Example 1. This gives amorphous mixtures 'single-phase TG = 65-67 ° C (10: 1 mixture) and TG = 61-63 ° C (5: 1 mixture) (compared to the following Table, samples a and b). Other single phase amorphous mixtures are obtained by the above method, 10 g each of a powder mixture placed in a boiling flask and homogenized during the melting process under nitrogen at Ti temperature. The mixtures are then cooled by a surface cooled to Tw under a standard atmosphere. The compound used, the test parameters and the resulting vitreous transition temperature Tg of the amorphous mixture are compiled in the following Table (amounts are given in percent by weight, based on the total weight of the mixture): Sample Compounds and amount Ti Tw Tg (° C) (° C) (° C) a) 9.1% cmpd. 16, 90.9% cmpd. 1 205 18 65-67 b) 16.7% cmpd. 16, 83.3% cmpd. 1 205 18 61-63 c) 16.7% cmpd. 16, 83.3% cmpd. 5 245 18 76-80 d) 50% cmpd. 16, 50% cmpd. 6 220 15 62-63 Sample Compounds and quantity Ti Tw Tg CC) (° C) (° C) e) 33.3% cmpd. 16, 66.7% cmpd. 6 225 15 76-79 f) 50"or cmpd 13 50% cmpd 2 165 15 48-49 g) 50% cmpd 13 50% cmpd 4 165 15 49-51 h) 50 or cmpd 13 50% cmpd 3 180 15 52-54 i) 50% cmpd 13 50% cmpd 5 245 15 62-63 j) 50% cmpd 13 50% cmpd 6 220 15 67-68 k) '50"or cmpd. 13 50% cmpd. 7 230 15 65-66 i) 50 o, "o cmpd 13 50 o," o cmpd. 10 140 15 45-46 m) 50% cmpd. 13 50% cmpd. 9 150 15 46-47 n) 50 o, or cmpd. 13 50% cmpd. 11 150 15 34-36 o) 50% cmpd. 13 50% cmpd. 1 200 15 56-57 ol) 50 or cmpd. 13 50 o, "o cmpd 12 135 13 33-34 o2) 50% cmpd 13 50 o, or cmpd 19 125 13 42-44 o3) 50% cmpd 13 50 o, * o cmpd 15 205 18 60-61? 4) 50% cmpd. 13 50 o, "o cmpd. B 135 18 40-41 or 5) 10% cmpd. 13 90 o. cmpd. 16 195 15 39-40 06) 30% cmpd. 13 70 o, "o cmpd 16 190 15 39-40 7) 50% cmpd 13 50% cmpd 16 190 15 41-42 08) 70 o, "o cmpd. 13 30 o," or cmpd. 16 170 15 44-45 o9) 90% cmpd. 13 10% cmpd. 16 140 15 45-46 Rl 33.3% cmpd. A, 66.7% cmpd. 220 15 35-36 Sample Compounds and quantity Ti Tw Tg CO (° c) (°? Q) 15% cmpd. 12; 28.3% cmpd. 13; 56.7% cmpd.16 200 18 38-39 r) 15% cmpd. 12; 42.5% cmpd. 13; 42.5% cmpd.16 200 18 40-41 s) 15% cmpd. 12; 56.7% cmpd. 16; 28.3% cmpd.6 200 18 57-59 t) 15% cmpd. 12; 42.5% cmpd. 16; 42.5% cmpd.6 225 18 56-57 compound A is bis (2, 2, 6, 6-tetramethylpiperidin-4-yl) sebacate compound B is a phosphonite mixture (CAS-no 119345-01-6, see introduction examples) Example 5a: Compound color stabilization Some of the amorphous mixtures prepared according to Example 5 and comprising compound 13, are subjected to a color stability test. For this purpose, the samples listed in the following Table are exposed to daylight in a closed glass container under atmospheric conditions. The pure amorphous compound 13 serves as a comparison. After the indicated storage time, the discoloration of the sample is estimated visually: Sample 1 Week 1 Month 2 Months Storage time compound 13 colorless green green yellowish f) colorless violet violet g) colorless green light green h) colorless green pale green i) colorless green pale green yellowish j) colorless green pale green k) colorless green pale yellowish green n) colorless yellow pale yellow o) colorless yellow yellow ol) colorless colorless 02) colorless yellow yellow color? 3) colorless colorless colorless? 4) colorless colorless colorless o5) colorless white * white * 06) colorless white * white *? 7) colorless colorless colorless 08) colorless colorless colorless o9 colorless colorless q colorless colorless r colorless colorless Begin recrystallization of compound no. 16 When stored, samples ol, o3-o9, qyr, which are stabilized in color according to this invention show a tendency to discoloration markedly lower than the pure compound 13 or that its mixtures with stabilizers different from phosph (on) itos or benzofuranones. Example 6: Use of sub-cooled fusions for the preparation of granules A pulverulent mixture A (resp. B) consisting of compounds 13, 12 and 16 (mixing ratios: see Table 6b) is added gravimetrically at a yield of 20%. kg / ha a twin-screw extruder of labotary (type Bühler DNDF 44). The spindle diameter is 44 mm, the length / diameter ratio (L / D) is 24 to 6 barrels, rotational speed of the spindles 100 min The barrels of the laboratory extruder are tempered (temperature profile: see Table 6a), such that only part of the dust (about 30% by weight) is fused to barrel 4 at a composition temperature of 130 ° C. The fusion thus obtained consisting of compound 13 (p.f. = 115 ° C) and 12 (p.f. = 132 ° C) in a mixing ratio of 65:35 (resp. 75:25), it is of low viscosity and forms a simple microhomogeneous continuous phase, where cmpd. 16 (p.f. = 186 ° C) is dispersed as a crystalline phase.

As for barrel 5, the composition is subcooled to about 65 ° C (sub-cooled fusion component -2-5.30% by weight) and then forced into a platic state (Tg <T <melting point>. the continuous phase) through a heated die plate having 6 free holes of 2.5 mm each at a dynamic pressure of 10-12 bars, to give cuttable strands. The hot cutting by rotating blades at a cutting frequency of 80-100 s "1 (cut length 2-2.5 mm), first gives smooth granules (T> Tg), the solidification of which is carried out in a fluidized bed cooler with virtually no subsequent crystallization The granules that are obtained (see Table 6c) are low in dust and flowable and comprise a single phase amorphous component (22-27 wt.% according to DSC) which consists of compound 13 (55-65% by weight) and compound 12 (35-45% by weight) Another pulverulent mixture C (resp.D) consisting of compounds 12, 16 and 6 is processed as described above for mixtures A and B, but the addition is carried out at a yield of 22 kg / h and the rotational speed of the spindle is 50 min "1. The mixing ratios and temperature profile are found in Tables 6a and 6b; the properties of granules are compiled in Table 6c. Up to barrel 4, only part of the powder (approximately 30% by weight) is melted at a composition temperature of approximately 150 ° C. A low viscosity melt consisting of compound 12 (mp 132 ° C) and 16 (mp 186 ° C) at a mixing ratio of about 50:50 is obtained as a continuous phase, where compound 6 (mp 220 ° C) ) is dispersed. The composition is subcooled from 5 to aproximadmente barrel 120 ° C (subcooled melting component 20-25% by weight) and processed as described above at a dynamic pressure of 08.07 bars (mixture C) or 13 to 15 bars (mixture D) in strands pelletized to a cutoff frequency of 100 s "1. The compound 16 is subsequently crystallized into a fluidized bed cooler. The granules thus obtained (see Table 6c) are low, dust, and flowable component comprising an amorphous single phase (12-15% wt according to DSC), consisting of compound 12 (about 95% by weight) and compound 16 (about 5% by weight) Table 6a. profile temperature in the extruder; addition of powder in the barrel 1 Mix A Mix B Mix C Mix D barrel 1: water 18 ° C 18 ° C 18 ° C 18 ° C barrels 2 + 3: oil 140 ° C 130 ° C 160 ° C 160 ° C Table 6a: Temperature profile in the extruder; addition of powder in the barrel 1 Mix A Mix B Mix C Mix D barrel 4: oil 130 ° C 130 ° C 160 ° C 160 ° C barrel 5: water 18 ° C 18 ° C 100 ° C 70 ° C (steam) barrel 6: water 18 ° C 18 ° C 100 ° C 105 ° C (steam) (steam) Matrix plate: oil 80 ° C 80 ° C 130 ° C 130 ° C Table 6: Physical-chemical composition of the granules (amounts in% by weight) Comp. Comp. Comp. Comp. Total Analysis 13 12 16 6 DSCCO mixture A: amorphous phase 13-15-9-11% < 0.5% - 22-26% Tg = 38-39 crystalline phase 13-16% 56% 74-78% p.f. = 110; 166 total: 28.3% 15% 56.7? - 100% mixture B: amorphous phase 15-18% 7-9í < 0.5% - 23-27% Tg = 41-42 crystalline phase 24.5-27.5% 6-8% > 42% 73-77% p.f. = 102; 160 Table 6: Physical-chemical composition of the granules (amounts in% by weight) Comp. Comp. Comp. Comp. Total / Analysis 13 12 16 6 DSC O total 42.5% 15% 42.5% 100% mix C: amorphous phase 11-12% < 1% < 0.5% 11-13% Tg = 29-30 crystalline phase 3-4% > 56 > 28í 87-89% p.f. = 122; 160; 180-200 total: 15% 56.7% 28.3% 100% mixture D: amorphous phase 13.5-14.5% < 1% < 0.5% 14-15% Tg = 30-31 crystalline phase 0.5-1.5% > 41.5% > 42% 75-76% p.f. = 120, -163; 170-200 total: 15% 42.5% 42.5% 100% Table 6c: Properties of the granules Mixture: A C and D - particle size (mm, min.-max dimension): 1.5-3.5 1.5-3.5 1.5-3.5 - bulk density (kg / 1): 0.52-0.57 0.51-0.56 0.53-0.56 Table 6c: Properties of the granules Mixture: A B_ C and D - angle of repose - (°, norm DlN-lSO 4324): 37 38 35 - flow time - (s; DIN 53492; 15 mm) 10 10.5 10 - dust formation (% by weight after 5 min, Heubach test): 0.22 0.26 0.24 - maximum storage temperature (° C): 35 35 30 Example 7: Preparation of the β-form of compound No. 14 by fluidized-bed granulation 2 Kg of -2- (2-hydroxy-3,5-di-ter) -butylphenyl) -5-chlorobenzotriazole (compound No. 14) are placed in a vessel at 190 ° C in the form of a melt and sprayed by a two fluid nozzle, in a fluidized bed consisting of 300 g of the ground compound 14 at an air velocity of 1-1.5 m / s. The product solidifies with formation of granules (agglomeration), which consist of more than 60% of the β form. Example 8: Preparation of the β-form of compound 14 by preparation to make fluid 2- (2-hydroxy-3,5-di-tert-butyl-phenyl) -5-chlorobenzotriazole (compound No. 14) is placed in a container in the form of a fusion and sprayed on the head of a preparation tower to make fluid and freeze solid with air at a temperature lower than 156 ° C and then removed at the foot of the tower. The product obtained consists of more than 60% by weight of the β form.

Example 9: Preparation of the ß form of compound 14 by quenching 100 g of 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole (compound No. 14) are maintained for 15 hours at 145 ° C in a laboratory vane dryer without adding any solvent. Subsequent x-ray examination shows that the product is obtained at more than 90% in the β-form. Example 10: Preparation of the β form of compound 14 by dissolution and recrystallization In a vane dryer, 1600 kg of 2- (2 -hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole (compound No. 14) are charged with 240 kg of xylene and the mixture is maintained for 5 h at a heating temperature of 145 ° C. Xylene is then removed by distillation and the contents of the dryer are cooled to 100 ° C, charged with 100 1 of water, which is then removed again by distillation and the product is dried. The product thus obtained consists completely of the β form.

At laboratory scale, 750 g of compound 14 are charged in a similar way with 250 g of 2-butanol and 150 g of xylene and the mixture is refluxed for 30 minutes, the internal temperature is 109 ° C, and then it is at 50 ° C by cooling, filtering and drying. The product thus obtained consists completely of the β form. Example 11: Preparation of the amorphous form of Compound No. 14 5 g of crystalline powdery ~ (2-hydroxy-3, 5-di-tert-butylphenyl) -5-chlorobenzotriazole (compound No. 14) are placed in a 10 ml test tube and heat under nitrogen in a drying oven. The powder turns to a pale yellow, clear, low viscosity melt after 10 to 15 minutes at 157 - 159 ° C. The melt is emptied in portions into a stainless steel plate cooled to 0 ° C and quickly becomes highly viscous and solidifies spontaneously. Nodules of part of the melt were prepared by dripping on the cooled steel plate. The vitreous composition can be easily separated from the cooling plate and sprayed in a cooled mortar. DSC confirms the amorphous structure, Tg = 22 ° C.

Claims (23)

1. RE1VI-PICATIONS 1. A process for the preparation of a low-powder stabilizer, comprising extruding a subcooled melt consisting essentially of one or more organic compounds having a molecular weight of 200 to 1500 g / mol, or the plastic composition consisting of the mixture of the subcooled melt and an additional component, which is chosen from sub-cooled melt compounds in crystalline form and other conventional additives.
2. 2. A process according to claim 1, characterized in that the molecular weight of each main component of the subcooled melt is 300-1200 g / mol.
3. 3. A method according to claim 1, characterized in that each main component of the subcooled fusion itself has a glass transition temperature (TG) in the range of 10-120 ° C.
4. 4. A process according to claim 1, characterized in that the subcooled melting component in the plastic composition is from 5 to 100% by weight.
5. 5. Granules obtained by a process according to claim 1.
6. 6. Use of a subcooled melt consisting of one or several organic compounds having a molecular weight of 200 to 1500 g / mol for extrusion, in particular for pelleting, melting granulation, pastillation or preparation of compound mixtures.
7. 7. A solid phase single amorphous stabilizer, comprising 2 or more compounds with a molecular weight in the range of 300-1000 g / mol.
8. 8. A sub-cooled or solid amorphous fusion of 2,2'-methylenebis (4- [1,1,3, 3-tetramethylbutyl] -6-benzotriazol-2-yl-f-enol); bis (2-methyl-4-hydroxy-5-tert-butylphenyl) sulfide; N, N '-bis (3- [3', 5 '-di-tert-butyl-4' -hydroxyphenyl] propionyl) hexa-methylenediamine; 1,3,5-trimethyl-2,4,6-tris (3 ', 5'-di-tert-butl-4' -hydroxybenzyl) benzene; 1, 3, 5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1 H, 3H, 5H) -frione; 1, 3, 5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) 1,3,5-triazin-2,4,6- (1 H, 3H, 5H) -frione; di (1, 2, 2, 6, 6-pentamethyl-piperidin-4-yl) -2- (3,5-di-tert-butyl-4-hydroxy-benzyl) -2-n-butyl-malonate; 2- (2 '-hydroxy-3', 5'-bis (1,1-dimethyl-benzyl) phenyl) -benzotriazole; 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole; 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole; an isomeric mixture of 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) - (9d) -2 (3H) -benzofuranone and 5,7-di-er-butyl-3 - (2, 3-dimethylphenyl) - (9d) -2 (3H) -benzofuranone; or of a compound of the formula
9. 9. A mixture comprising a subcooled or amorphous solid fusion of a compound according to claim 8, in an amount of 5 to 10% by weight.
10. A process for the preparation of a subcooled melt according to claim 8, or a mixture comprising a subcooled melt according to claim 9, which comprises rapidly cooling the melt at a temperature from the point of regular fusion to the glass transition temperature of the homogeneous phase.
11. 11. A process for the preparation of the amorphous solid according to claim 8, or a mixture comprising an amorphous solid according to claim 9, characterized in that it comprises using the subcooled melt or fusion at a temperature below the glass transition temperature.
12. 12. A crystalline ß modification of compound 14 where the interplanar spacings are 9.4 • 10 m, 4.69 • 10"10 m, 3.94 • 10" 10 m and 3.79 • 10"10 m
13. 13. A mixture consisting of different modifications of compound 14 of the formula comprising at least 40% by weight of the crystalline form β according to claim 12.
14. 14. A process for the preparation of the crystalline form β of the compound 14 according to claim 12, characterized in that it comprises crystallizing, recrystallizing, or temper compound 14 in the temperature range from 95 ° C to the melting point and then cool it rapidly.
15. 15. A procedure for color stabilization of pentaerythritol-tetrakis (3 - [3 ', Amorphous 5'-di-tert-butyl-4'-hydroxyphenyl] .- propionate), which comprises mixing a stabilizer of the class consisting of phosphites, organic phosphonites and / or benzofuran-2 -ones to a fusion consisting of pentaerythritol - tetrakis (3- [3 ', 5' -di-tert-butyl-4 '-hydroxyphenyl] -propionate) and solidify the mixture thus obtained.
16. 16. Used a stabilizer of the class consisting of phosphites, organic phosphonites and / or benzofuran-2-ones for color stabilization of pentaerythritol-tetrakis (3- [3 ', 5' -di-tert-butyl-4 '-hydroxyphenyl ] propionate) amorphous.
17. 17. A stabilizing composition, characterized in that it comprises: a) pentaerythritol-tetrakis (3- [3 ', 5' -di-tert-butyl-4 '-hydroxyphenyl] propionate), and b) at least one compound of the benzofuran-2 type -one
18. 18. A composition, characterized in that it comprises A) an organic material susceptible to thermal or / and actinic oxidative degradation or accumulation, and B) the amorphous form of a compound according to claim 8, the β-crystalline form of the compound 14 according to claim 13 and / or the stabilizer composition according to claim 17, as a stabilizer. "
19. 19. A method for stabilizing organic material against thermal or actinic oxidative degradation or accumulation, comprising adding to the material the amorphous form of a compound according to claim 8, the β-crystalline form of compound 14 according to claim 13 and / or the stabilizing composition according to claim 17, as a stabilizer.
20. 20. A process according to claim 19, characterized in that 0.01 to 15 parts by weight of the stabilizer are added to 100 parts by weight of organic material to be stabilized.
21. 21. A method according to claim 19, characterized in that the organic material is a synthetic thermoplastic polymer.
22. 22. A method according to claim 19, characterized in that one or more customary additives are added as additional components.
23. 23. Use of the amorphous form of a compound according to claim 8, of the β-crystalline form of the compound 14 according to claim 13 and / or of the stabilizing composition according to claim 17, for stabilizing organic material against oxidative, thermal or actinic accumulation or degradation.