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    • 专利摘要:
    The present invention relates to novel thermoplastic polymer blends containing polycarbonates, release agents and certain phosphites, and shaped bodies, in particular optical data storage media such as compact discs, video discs, digital multifunction discs, and other non-writable. It relates to the use of these polymer blends used to make optical data storage media or repeatable, for example erasable optical data storage media, and the moldings themselves which can be prepared from them.
    公开号:KR20030088470A
    申请号:KR10-2003-7012459
    申请日:2002-03-13
    公开日:2003-11-19
    发明作者:빌프리드 해세；제임스 메이슨
    申请人:바이엘 악티엔게젤샤프트；
    IPC主号:
    专利说明:

    New Polymer Blends {NOVEL POLYMER BLENDS}
    [1] The present application relates to novel thermoplastic polymer mixtures containing polycarbonates, release agents and certain phosphites, and shaped articles, in particular optical data carriers such as compact discs, video discs, digital multifunction discs, and one-time The above relates to the use of these polymer mixtures used to prepare additional optical data storage media that can be written and erased, and to the molded articles themselves which can be prepared from them.
    [2] Polycarbonates are commonly used as materials for injection molding or injection-press molding of optical data storage media because of certain combinations of properties such as transparency, heat resistance and dimensional stability. Additives such as release agents and stabilizers are added to the polycarbonates in order to improve processability generally occurring at temperatures in the range from 300 ° C to 400 ° C.
    [3] Aliphatic fatty acid esters of polyhydric alcohols such as esters of long chain fatty acids and glycerol and esters of long chain fatty acids and pentaerythritol are preferably used as release agents. These esters can also be partially esterified when they have free OH groups which are clearly advantageous for release action, but these esters impair the thermal stability of the mixture and require the addition of stabilizers. However, this stabilizer should be very effective, that is to say effective at very low concentrations because otherwise there is a risk of coating formation in the mold. In this case, the molds and dies often have to be cleaned during processing, which is harmful and results in sheets of inferior quality. On the other hand, fully esterified release agents have higher stability, but at low concentrations the release behavior of these esters is much weaker than esters with free OH groups. Therefore, fully esterified release agents should generally be used in higher amounts, which increases the risk of coating formation, while the amount of stabilizer added on the other hand may be somewhat smaller.
    [4] Multiple mixtures are already presented in the literature as follows:
    [5] In order to stabilize a mixture containing a release agent with OH groups, EP-A 205 192 describes the use of a mixture of trimethyl phosphate and / or triethyl phosphate mixed with phosphite. Thus, the stabilizing effect of phosphate esters or phosphites alone is inadequate and these phosphate esters are ecologically undesirable.
    [6] JP-A 62184639 describes an optical data memory made from phosphite stabilized polycarbonate. Easily volatilized phosphites, for example trimethyl phosphite, are preferred, which is ecologically undesirable and critical to coating formation.
    [7] JP-A 2000080261 describes a release agent, tris (di-tert-butyl-phenyl) phosphite and a mixture of phosphoric acid and polycarbonate. Thus, the stabilizing effect of phosphite is insufficient so that phosphoric acid is used as an additional stabilizer, but may cause corrosion of the memory layer on the optical data storage medium under conditions of high atmospheric humidity and elevated temperature.
    [8] It was therefore an object to develop thermoplastic polymer mixtures containing polycarbonates, mold release agents and heat stabilizers which, in other words, have good release properties in small amounts, for example, which are optimized for the production of optical data storage media and other shaped articles. In particular, new disc formats with higher storage capacities and optionally thinner discs, such as digital multifunction discs (DVDs), require higher thermal stability than CDs. Damage to the material and coating formation in the mold become more dangerous during processing into the molded article.
    [9] In the case of mixtures according to the invention, this object is surprisingly achieved by the improved quality of the data memory and the improved processability of the material during injection molding or injection pressing molding.
    [10] The present application therefore relates to a thermoplastic polymer mixture containing at least one polycarbonate, at least one release agent and at least one phosphite having a particular chemical structure. These phosphites stabilize the release agents present, even at low concentrations, and can therefore lower the amount of release agents having the same release action. The coating formation is therefore surprisingly low due to the reduction in the use of release agents and also their surprisingly increased stability.
    [11] The invention also provides for the use of these polymer mixtures used to make optical data storage media such as compact discs, video disks, digital multifunction disks and other optical data storage media that can be written or erased more than once, and polymer polymers prepared from To an optical data storage medium itself.
    [12] Polymer mixtures can also be used in other traditional polycarbonate applications, clearly including using polycarbonates with higher molecular weights. This application covers food and beverage packaging, optical lenses and prisms, lenses for lighting purposes, automotive headlight lenses, transparencies for architectural and automotive, transparencies for different types, for example greenhouses, so-called double wall sheets or hollow chamber sheets. It may be transparent or opaque, such as Other examples of applications include any type, for example medical instruments, household appliances, such as juice presses, coffee machines, mixers; For office equipment such as computers, monitors, printers, copiers; For sheets, pipes, electrical installation ducts, windows, doors and profiles for the building industry, interior finishing and exterior applications; In the field of electrical engineering, for example housing components, films, profiles for switches and plugs. Molded articles according to the invention can also be used in truck body parts and in component parts and interior finishes of railway vehicles, ships, aircraft, buses and other motor vehicles.
    [13] In the present invention, the thermoplastic polymer mixture contains mainly aromatic polycarbonates. The term polycarbonate includes both homopolycarbonates and copolycarbonates, and the polycarbonates may be branched or linear in a known manner. They have an average molecular weight of 5,000 to 80,000, preferably 10,000 to 40,000 as measured by gel permeation chromatography. Particular preference is given to molecular weights between 15,000 and 35,000, in particular between 15,000 and 22,000.
    [14] These polycarbonates are prepared in a known manner from diphenols, carbonic acid derivatives, optionally chain stoppers and optionally branching agents.
    [15] Details regarding the preparation of polycarbonates have been described in many patents over about 40 years. In this application only by way of example, Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964; Dr. Freitag, U. Grigo, P.R. Muller, H. Nouvertne ', BAYER AG, "Polycarbonates" in Encyclopedia of Polymer Science and Engineering, Volume 11, Second Edition, 1988, pages 648-718; And finally Dres. U. Grigo, K. Kirchner and P.R. Muller "Polycarbonate" in Becker / Braun, Kunststoff-Handbuch, Vol. 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag, Munich, Vienna 1992, pages 117-299.
    [16] Examples of suitable diphenols for the production of polycarbonates include hydroquinone, resorcinol, dihydroxyphenyl, bis- (hydroxyphenyl) -alkane, bis- (hydroxyphenyl) -cycloalkane, bis- (hydroxy Phenyl) -sulfide, bis- (hydroxyphenyl) -ether, bis- (hydroxyphenyl) -ketone, bis- (hydroxyphenyl) -sulfone, bis- (hydroxyphenyl) -sulfoxide, α-α '-Bis- (hydroxyphenyl) -diisopropylbenzene, and nucleo-alkylated and ring-halogenated compounds.
    [17] Preferred phenols include 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -p-diisopropyl-benzene, 2,2-bis- (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis- (3 -Chloro-4-hydroxyphenyl) -propane, bis- (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl)- Propane, bis- (3,5-dimethyl-4-hydroxyphenyl) -sulfone, 2,4-bis- (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,1-bis -(3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 4,4 '-(m- Phenylenediisopropylidene) -diphenol.
    [18] Particularly preferred diphenols include 2,2-bis- (4-hydroxyphenyl) -propane (BPA), 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2- Bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane, 4,4 '-(m- Phenylenediisopropylidene) bisphenol (CAS-No. 13595-25-0) (BPM), 1,1-bis- (4-hydroxyphenyl) -cyclohexane and 1,1-bis- (4-hydroxy Phenyl) -3,3,5-trimethylcyclohexane (TMC) is mentioned.
    [19] These and further suitable diphenols are described, for example, in US 3 028 635, 2 999 835, 3 148 172, 2 991 273, 3 271 367, 4 982 014 and 2 999 846, DE-A 1 570 703, 2 063 050, 2 036 052, 2 211 956 and 3 832 396, in French patents 1 561 518, in the major thesis ["H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964"] and JP-A 62039/1986, 62040/1986 and 105550/1986.
    [20] Only one diphenol is used for homopolycarbonates and multiple diphenols are used for copolycarbonates.
    [21] With diol units selected from the group consisting of BPA and / or trimethylcyclohexyl-bisphenol (TMC), preferably comprising a homopolymer of BPA, a copolymer of BPA and TMC or a copolymer of 5 to 60% by weight of TMC Polymer mixtures containing at least one polycarbonate are preferably used.
    [22] Examples of suitable carbonic acid derivatives include phosgene or diphenylcarbonate.
    [23] Suitable chain stoppers include monophenols as well as monocarboxylic acids. Suitable monophenols are phenol itself, alkyl phenols such as cresol, p-tert.-butylphenol, pn-octylphenol, p-iso-octylphenol, pn-nonylphenol and p-iso-nonylphenol, p- Cumylphenol, halogen phenols such as p-chlorophenol, 2,4-dichlorophenol, p-bromophenol amylphenol and 2,4,6-tribromophenol and mixtures thereof.
    [24] Preferred chain stoppers are phenols of formula (I)
    [25]
    [26] In the above formula,
    [27] R represents hydrogen, tert-butyl or branched or unbranched C 8 and / or C 9 alkyl radicals. However, p-cumylphenol can also be preferably used. In the case of the transesterification process, the chain stopper is generated from the diaryl carbonate used.
    [28] Preferably the amount of chain stopper used in the phase interface method is from 0.1 mol% to 5 mol%, respectively, based on the moles of diphenols used. Chain stoppers can be used before, during or after phosgenation.
    [29] Suitable branching agents are those having at least trifunctional compounds, in particular at least three phenolic OH groups, known from polycarbonate chemistry.
    [30] Examples of suitable branching agents are phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2, 4,6-dimethyl-2,4,6-tri -(4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- ( 4-hydroxyphenyl) -phenylmethane, 2,2-bis- [4,4-bis- (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis- (4-hydroxyphenyl- Isopropyl) -phenol, 2,6-bis- (2-hydroxy-5'-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxy Phenyl) -propane, hexa- (4- (4-hydroxyphenyl-isopropyl) -phenyl-orthoterephthalic acid ester, tetra- (4-hydroxyphenyl) -methane, tetra- (4- (4-hydroxyphenyl -Isopropyl) -phenoxy) -methane and 1,4-bis- (4 ', 4 "-dihydroxytriphenyl) -methyl) -benzene, as well as 2,4-dihydroxybenzoic acid, trimesic acid , Cyanuric chloride and for some applications preferably 3,3-bis- (3-methyl-4-hydride Oxy-phenyl) -2-oxo-2,3-dihydroindole is mentioned.
    [31] The amount of branching agent optionally used is from 0.01 mol% to 2 mol%, respectively, based on the moles of diphenols used.
    [32] Branching agents may be present in the aqueous interface with diphenols and chain stoppers in the aqueous alkaline phase or dissolved in organic solvents. For the transesterification process, branching agents can be used with the diphenols.
    [33] One of ordinary skill in the art is familiar with all these methods of making thermoplastic polycarbonates.
    [34] The compound used as the release agent is preferably an ester of a long chain carboxylic acid and a polyhydric alcohol. Release agents that are fully esterified and have free OH groups are preferred. Particular preference is given to (partial) esters of glycerol, trimethylol propane, pentaerythritol or similar polyhydric alcohols with saturated monovalent fatty acids having from 16 to 22 carbon atoms. In particular, glycerol monostearate and glycerol monopalmitate are preferred.
    [35] Saturated monovalent fatty acid esters of these glycerols are used alone or as a mixture with two or more components. Saturated monoesters of glycerol are generally prepared by transesterification of cured animal or vegetable oils with glycerol. Although the reaction product may also contain esters other than glycerol esters, it is used as a release agent according to the invention. For example, the mixture may contain smaller or larger proportions of diglycerides and triglycerides.
    [36] The optimal amount of release agent during the manufacture of CDs and other optical storage media (such as DVDs) is determined on the one hand by the appropriate release action and on the other by the formation of a coating on the mold. Commonly used concentrations of release agents are between 50 and 1,000 ppm, more advantageously between 100 and 500 ppm. For other applications of polycarbonate, the concentration is between 100 and 10,000 ppm, preferably between 2,000 and 7,000 ppm.
    [37] Special phosphites according to the invention have both aromatic and aliphatic radicals in the molecule. These are compounds having the formula:
    [38]
    [39] In the above formula,
    [40] n represents the number 0-5, preferably 1-3, and very preferably 3,
    [41] Y independently of each other at each occurrence represents an alkyl or optionally substituted aryl, preferably C 1 -C 4 alkyl, particularly preferably methyl, sec-butyl and tert-butyl,
    [42] m represents a number from 1 to 3, preferably 3, and
    [43] X represents, in each case independently, an optionally substituted methylene radical, wherein at least one methylene radical must be completely substituted and the substituents are independently of each other a group comprising C 1 -C 20 alkyl, preferably C 1 -C Two substituents of methylene radicals selected from or completely substituted with 20 alkyl together represent the following radicals:
    [44]
    [45] R 1 is selected from the group comprising C 1 -C 18 alkyl, C 3 -C 12 cycloalkyl, C 6 -C 30 alkaryl and aryl, these radicals again being 1 to 4 O-alkylene-O and (Or) carboxylic ester-COO-radicals; C 2 -C 18 polyhydroxyalkyl containing 2 to 10 hydroxyl groups; It may be substituted by a C 2 -C 18 polyphenyl radical containing 2 to 10 phenolic OH groups.
    [46] Preferred compounds have the formula:
    [47]
    [48] In the above formula,
    [49] R 2 represents C 1 -C 6 alkyl,
    [50] R 3 represents methyl or ethyl, and
    [51] R 4 is selected from the group comprising C 1 -C 18 alkyl, C 3 -C 12 cycloalkyl, C 6 -C 30 alkaryl and aryl, these radicals again being 1 to 4 O-alkylene-O and (Or) carboxylic ester-COO-radicals; C 2 -C 18 polyhydroxyalkyl containing 2 to 10 hydroxyl groups; It may be substituted by a C 2 -C 18 polyphenyl radical containing 2 to 10 phenolic OH groups.
    [52] Also preferred are compounds having the formula:
    [53]
    [54] In the above formula,
    [55] Y and n have the above meanings, and
    [56] R 5 is independently from each other selected from the group comprising hydrogen and C 3 -C 20 alkyl, at least one R 5 preferably represents alkyl,
    [57] R 6 independently of one another represents C 1 -C 10 alkyl.
    [58] Particular preference is given to compounds having the formula wherein R 1 and R 2 represent methyl, sec-butyl or tert-butyl.
    [59]
    [60] Similarly, the compounds defined on pages 16-20 of EP A1 0 038 876 and the examples mentioned on page 21 of the same document are also particularly preferred.
    [61] Very particular preference is given to (2,4,6-tri-t-butylphenyl)-(2-butyl-2-ethyl-propane-1,3-diyl) -phosphite having the formula:
    [62]
    [63] Phosphite may be used alone, but may also be used in combination with other phosphorus compounds, where the other phosphorus compounds may also have different phosphorylation numbers. Thus, for example, a combination of other phosphites, phosphines such as triphenylphosphine, phosphonites, phosphates, phosphonates and the like and the phosphites according to the invention can be used.
    [64] The phosphites used according to the invention can be prepared in a generally known or similarly known manner. (2,4,6-tri-t-butylphenyl)-(2-butyl-2-ethyl-propane-1,3-diyl) -phosphite is described, for example, in EP-A 702018 and EP 635514. .
    [65] The polymer mixtures according to the invention generally contain phosphorus compounds in proportions of 10 to 5,000 ppm, preferably 10 to 1,000 ppm, particularly preferably 20 to 500 ppm and most preferably 50 to 250 ppm.
    [66] Preferred, particularly preferred or very preferred compounds with the substituents mentioned below are preferred, particularly preferred or very preferred.
    [67] However, the definition or description of quantitative ratios or parameters and radicals previously mentioned in general or as preferred ranges may optionally be combined with each other between the respective ranges and preferred ranges.
    [68] The release agent and the phosphorus compound are added to the thermoplastic polymer mixture, for example, and preferably after the preparation and during the treatment of the polycarbonate, for example by adding the thermoplastic polymer mixture to the melt or to the polycarbonate polymer solution. It is added in the polymer mixture. In addition, as long as all components are contained during the production of the final product (molded product), the components can be added independently of one another in various working steps, for example one of the components during the treatment of the polymer solution and the other ) Can be added in the melt.
    [69] The thermoplastic polymer mixtures according to the invention may also contain known amounts of conventional additives for polycarbonates, for example and preferably UV stabilizers, flame retardants, dyes, fillers, foaming agents, optical brighteners And antistatic agents. In the optical field, it is desirable to use components that do not adversely affect the transparency of the material.
    [70] These materials can be found in many publications, such as Additives for Plastics Handbook, John Murphy, 1999, and are commercially available.
    [71] 1. Examples of suitable antioxidants:
    [72] 1.1 alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol , 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- ( α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4- Methoxymethylphenol, nonylphenol having a linear or branched side chain, 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.
    [73] 1.2 alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6- Ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.
    [74] 1.3 hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6 -Diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,6-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.
    [75] 1.4 Tocopherols , for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).
    [76] 1.5 hydroxylated thiodiphenylethers such as 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4 ' -Thiobis (6-tert-butyl-3-methyl-phenol), 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.
    [77] 1.6 alkylidenebisphenols such as 2,2'-methylenebis- (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2 , 2'-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butyl-phenol), 2,2'-ethylidenebis (4,6-di-tert-butyl Phenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2, 2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5- Methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl 4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, at Lenglycolbis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methyl-phenyl] terephthalate, 1,1-bis (3,5-dimethyl 2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy- 2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) -pentane.
    [78] 1.7 O-, N- and S-benzyl compounds , for example 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzylether, octadecyl-4-hydroxy -3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl ) Amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, iso Octyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
    [79] 1.8 hydroxybenzylated malonates such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert -Butyl-4-hydroxy-5-methylbenzyl) malonate, dododecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4 -(1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.
    [80] 1.9 aromatic hydroxybenzyl compounds , for example 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4- Hydroxybenzyl) -phenol.
    [81] 1.10 triazine compounds , 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-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis ( 3,5-di-tert-butyl-4-hydroxy-phenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxy Phenoxy) -1,2,3-triazine, 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl)- 1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3 , 5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
    [82] 1.11 acyl amino phenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.
    [83] 1.12 esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols , for example methanol, ethanol, n-octanol, i-octanol, octadecanol , 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy Ethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1- Esters with phospha-2,6,7-trioxabicyclo [2.2.2] octane, particularly well suited and preferably with octadecanol Irganox, manufactured by Ciba Spec. (IRGANOX) 1076®.
    [84] 1.13 esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols , for example methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl Isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxy-methyl-1- Ester with phospha-2,6,7-trioxabicyclo [2.2.2] octane.
    [85] 1.14 esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols , for example methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1 , 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7- Ester with trioxabicyclo [2.2.2] octane.
    [86] 1.15 Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with monohydric or polyhydric alcohols , for example methanol, ethanol, 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-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxa Bicyclo [2.2.2] octane.
    [87] 1.16 Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid , for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropy Onyl) 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- (3,5-di-tert-butyl-4-hydroxyphenyl] -propionyloxy) ethyl] oxa Meade (Naugard® XL-1, manufactured by Uniroyal).
    [88] 1.17 Ascorbic Acid (Vitamin C)
    [89] 1.18 amine-containing antioxidants such as N, N'-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1 , 4-dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methyl-heptyl)- p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p- Phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methyl-heptyl ) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl-N , N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-iso-propoxy-diphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-di-tert-octyl-diphenylamine, 4-n-butyl-aminophenol, 4-butyrylaminophenol, 4-nonanoyl-aminophenol, 4-dodecanoyl-aminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) Amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-Tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenyl-amino) propane, (o-tolyl) biguanide, A mixture of bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, mono- and dialkylated tert-butyl / tert-octyl diphenyl amine, Mixtures of mono- and dialkylated nonyldiphenylamines, Mixtures of mono- and dialkylated dodecyldiphenylamines, Mixtures of mono- and dialkylated isopropyl / isohexyldiphenylamines, Mono- and dialkylated tert-butyl diphenyls Mixture of amines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothione A mixture of gin, mono- and dialkylated tert-butyl / tert-octyl phenothiazine, tert-octylphenothiazine, a mixture of mono- and dialkylated tert-octylphenothiazine, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperid-4-yl) hexamethylenediamine, Bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetra- Methylpiperidin-4-ol. Each compound or mixture thereof can be used.
    [90] 1.19 Suitable thiosynergists include, for example, dilaurylthiodipropionate and / or distearylthiodipropionate.
    [91] 2. UV-absorbers and light stabilizers can be used in the compositions according to the invention in amounts of 0.1 to 15% by weight, preferably 3 to 8% by weight, based on the weight of the composition. Examples of suitable UV absorbers and light stabilizers include the following:
    [92] 2.1 2- (2'-hydroxyphenyl) benzotriazole, for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert- Butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '-(1,1 , 3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotria Sol, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis (α, α-di-methylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-( 2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethyl-hexyloxy) carbonylethyl] -2' -Hydroxyphenyl) -5-chlorobenzotriazole , 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2 '-Hydroxy-5'-(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-octyl-oxycarbonyl Ethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl ) Phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; polyethylene glycol 300 and 2- [3 transesterification product of '-tert-butyl-5'-(2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole [R-CH 2 CH 2 -COO-CH 2 CH 2 ] 2 (where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl), 2- [2'-hydroxy-3 '-(α , α-dimethylbenzyl)- 5 '-(1,1,3,3-tetramethylbutyl) phenyl] benzotriazole, 2- [2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl) -5 ' -(α, α-dimethylbenzyl) phenyl] benzotriazole.
    [93] 2.2 2-hydroxybenzophenones such as 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2 ', 4'-trihydroxy- and 2'-hydroxy-4,4'-dimethoxy derivatives.
    [94] 2.3 Esters of substituted and unsubstituted benzoic acid , for example 4-tert-butylphenylsalicylate, phenylsalicylate, octylphenylsalicylate, bibenzoylresorcinol, bis (4-tert-butylbenzoyl) rezo Lecinol, benzoylresorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4 -Hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl -4-hydroxybenzoate.
    [95] 2.4 acrylates such as ethyl-α-cyan-β, β-diphenylacrylate, isooctyl-α-cyan-β, β-diphenylacrylate, methyl-α-carbomethoxycinnamate, methyl -α-cyan-β-methyl-p-methoxycinnamate, butyl-α-cyan-β-methyl-p-methoxycinnamate, methyl-α-carbomethoxy-p-methoxycinnamate and N- (β-carbomethoxy-βcyanvinyl) -2-methylindolin.
    [96] 2.5 Nickel compounds , for example nickel complexes of 2,2'-thiobis [4- (1,1,3,3-tetramethylbutyl) phenol], for example further ligands, for example n- 1: 1 or 1: 2 complex, nickel dibutyldithiocarbamate, 4-hydroxy-3,5-di-tert-butyl with or without butylamine, triethanolamine or N-cyclohexyldiethanolamine Monoalkyl esters of benzylphosphonic acid, for example nickel salts of methyl or ethyl esters, ketoximes, for example nickel complexes of 2-hydroxy-4-methylphenylundecylketoxime, with or without additional ligands Nickel complex of -phenyl-4-lauroyl-5-hydroxypyrazole.
    [97] 2.6 sterically hindered amines such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) Succinate, bis (1,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) seva Kate, bis (1,2,2,6,6-pentamethyl-4-piperidyl), n-butyl-3,5-di-tert-butyl-4-hydroxy-benzylmalonate, 1- ( Condensate of 2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, N, N'-bis (2,2,6,6-tetramethyl-4 Linear or cyclic condensates of -piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethyl- 4-piperidyl) nitrilotriacetate, tetrakis- (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 1,1 ' -(1,2-ethanediyl) bis- (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpipepe Dine, 4-stearyl-oxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane -2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperi Dill) succinate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5 Linear or cyclic condensates of triazines, 2-chloro-4,6-bis (4-n-butyl-amino-2,2,6,6-tetramethylpiperidyl) -1,3,5-tri Condensates of azine and 1,2-bis (3-aminopropyl-amino) ethane, 2-chloro-4,6-bis (4-n-butylamino-1,2,2,6,6-pentamethylpy Condensates of ferridyl) -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] de -2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) -pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, 4-hexadecyloxy- and 4-stearyloxy-2,2,6, Mixture of 6-tetramethylpiperidine, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro- Condensation products of 1,3,5-triazine, 1,2-bis (3-aminopropylamino) -ethane and 2,4,6-trichloro-1,3,5-triazine and 4-butylamino- Condensation products of 2,2,6,6-tetramethylpiperidine (CAS Registry No. [136504-96-6]); N- (2,2,6,6-tetra-methyl-4-piperidyl) -n-dodecyl-succinimide, N- (1,2,2,6,6-pentamethyl-4-pi Ferridyl) -n-dodecyl-succinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospyro [4.5] decane, 7 , 7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospyro [4.5] decane and epichlorohydrin reaction product, 1,1-bis ( 1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethene, N, N'-bis (formyl) -N, N'- Bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine, 1,2,2,6,6-pentamethyl-4-hydroxypiperidine and 4-methoxymethylene Diesters of malonic acid, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, 2,2,6,6-tetramethyl-4 Reaction product of aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine with malonic anhydride-α-olefin-copolymer.
    [98] 2.7 oxamides , for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-di-octyloxy-5,5'-di-tert- Butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanide, N, N'-bis (3-dimethyl Aminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide , a mixture of o- and p-methoxy-disubstituted oxanilides and a mixture of o- and p-ethoxy-disubstituted oxanilides.
    [99] 2.8 2- (2-hydroxyphenyl) -1,3,5-triazine , for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-tri Azine, 2- (2-hydroxy-4-octyloxyphenyl-4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl ) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4- Dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxy Phenyl) -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-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6, bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydrate Hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy ) Phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl- 1,3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2- Hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl)- 6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] phenyl} -4,6 Bis (2,4-dimethylphenyl) -1,3,5-triazine.
    [100] Each compound or a mixture thereof can be used.
    [101] 3. Suitable metal inerts are , for example, N, N'-diphenyloxamide, N-salicyl-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N '-Bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyldihydrazide , Oxanilide, isophthaloyldihydrazide, sebacoylbisphenylhydrazide, N, N'-diacetyladifoyldihydrazide, N, N'-bis (salicyloyl) oxalyldihydrazide, N, N'-bis (salicyloyl) thiopropionyldihydrazide. Each compound or a mixture thereof can be used.
    [102] 4. Suitable peroxide collectors are , for example, esters of β-thiodipropionic acid, for example lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazoles or 2-mercaptobenziimi Zinc salt of dozol, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (dodecyl mercapto) propionate. Each compound or a mixture thereof can be used.
    [103] 5. Suitable basic co-stabilizers are , for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallycyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts, higher fatty acids Alkaline earth metal salts of, for example, calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate. Each compound or a mixture thereof can be used.
    [104] 6. Suitable nucleating agents are , for example, inorganic materials such as talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably phosphates of alkaline metals, Carbonates or sulfates; Organic compounds such as mono or polycarboxylic acids and salts thereof such as 4-tert-butylbenzoic acid, adipic acid, diphenyl acetic acid, sodium succinate or sodium benzoate; Polymeric compounds such as ionic copolymers (ionomers). 1,3: 2,4-bis- (3'4'-dimethylbenzylidene) sorbitol, 1,3: 2,4-di (paramethyldibenzylidene) sorbitol and 1,3: 2,4-di ( Benzylidene) sorbitol is particularly preferred. Each compound or a mixture thereof can be used.
    [105] 7. Suitable fillers and reinforcing agents include, for example, calcium carbonate, silicates, glass fibers, glass balloon flasks, asbestos, talc, kaolin, mica, barium sulphate, metal oxides and hydroxides, carbon black, graphite, Fibers of wollastonite, sawdust and dust or other natural products, including synthetic fibers. Each compound or a mixture thereof can be used.
    [106] 8. Suitable further additives include, for example, plasticizers, lubricants, emulsifiers, pigments, viscosity modifiers, catalysts, flow regulators, optical brighteners, flame retardants, antistatic agents and blowing agents.
    [107] 9. Suitable benzofuranones and indolinones are described, for example, in US Pat. Nos. 4,325,863; U.S. Patent 4,338,244; U.S. Patent 5,175,312; U.S. Patent 5,216,052; U.S. Patent 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; As described in 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) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl-benzofuran-2-one, 3 -(4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5 , 7-di-tert-butylbenzofuran-2-one, 3- (3,4-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (2,3-dimethyl Phenyl) -5,7-di-tert-butylbenzofuran-2-one, including the formula (8) and a lactone antioxidant.
    [108]
    [109] These compounds, for example, act as antioxidants. Each compound or a mixture thereof can be used.
    [110] 10. Suitable fluorescent plasticizers are listed in "Plastics Additives Handbook", edited by R. Gachter and H. Muller, Hanser Verlag, 3rd edition, 1990, pages 775-789.
    [111] 11. Suitable flame retardant additives are phosphate esters, ie triphenylphosphate, resorcinol diphosphate esters, bromine containing compounds such as brominated phosphate esters, brominated oligocarbonates and polycarbonates, as well as salts, for example C 4 F 9 SO 3 - Na + .
    [112] 12. Suitable toughening agents include butadiene rubber grafted with styrene acrylonitrile or methyl methacrylate, ethylene / propylene rubber grafted with maleic anhydride, methyl methacrylate or styrene acrylonitrile Interpenetrating siloxane and acrylate networks grafted with ethyl and butyl acrylate rubbers, methylmethacrylate or styrene acrylonitrile.
    [113] 13. Suitable polymers are SAN, ABS, PMMA, PTFE, PSU, PPS, polyolefins such as polyethylene, polypropylene and ethylene / propylene rubber, epoxy resins, polyesters such as PBT, PET, PCT, PCTG and PETG As well as other polycarbonates produced by the interfacial method.
    [114] 14. Suitable antistatic agents include sulfonate salts, for example tetraethylammonium salts of C 12 H 25 SO 3- or C 8 F 17 SO 3- .
    [115] 15. Suitable colorants include pigments, as well as organic and inorganic dyes.
    [116] 16. Epoxy group-containing compounds such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, glycidyl methacrylate and copolymers of epoxy silanes.
    [117] 17. Compounds, anhydride groups such as maleic anhydride, succinic anhydride, benzoic anhydride and phthalic anhydride.
    [118] 18. Suitable phosphites and phosphonites as stabilizers include, for example, triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tris (nonylphenyl) phosphite, trilaurylphosphite, triocta Decylphosphite, distearylpentaerythritoldiphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritoldiphosphite, bis- (2,4, -di-tert- Butylphenyl) pentaerythritoldiphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritoldiphosphite, diisodecyloxypentaerythritoldiphosphite, bis (2,4-di-tert -Butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl) pentaerythritoldiphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4- Di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,1 0-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphosine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12- Methyl-dibenz [d, g] -1,3,2-dioxaphosphosine, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bis- (2,4-di- tert-butyl-6-methylphenyl) ethylphosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenz [d, g] -1,3,2-dioxa Phosphosine, 2,2 ', 2 "-nitrilo [triethyltris (3,3', 5,5'tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite ], 2-ethyl-hexyl- (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite, 5-butyl-5-ethyl 2- (2,4,6-tri-tert-butylphenoxy) -1,3,2-dioxaphosphyran, each compound or mixture thereof may be used.
    [119] Particular preference is given to tris (2,4-di-tert-butylphenyl) phosphite (Irgafos® 168, Ciba-Geigy) or triphenylphosphine.
    [120] Compounds in groups 16 and 17 act as melt stabilizers. These can be used individually or in mixtures.
    [121] Of the above additives, one of ordinary skill in the art can select a suitable additive that obviously does not impair transparency for application in the field of CD, DVD and other optical recording media.
    [122] Especially suitable additives are the benzotriazoles from Irganox 1076® and Group 2.1 (so-called Tinuvin), in particular mixed with one another.
    [123] The polymer mixtures according to the invention are used in known manner for the production of shaped articles, preferably for optical media, in particular compact discs and DVDs, as well as for polycarbonate for the production and rewriting of optical media one or more times. The writable layer is specifically composed of a dye or metal layer, the latter of which uses a change from an amorphous state to a crystalline state as a recording principle or has magnetic properties.
    [124] The preparation of such optical media preferably takes place from the pre-made polymer mixtures according to the invention, which occur for example as granules. However, optical media can also be prepared by incorporating the components in pure or conventional commercially available polycarbonates and / or customary additives during the production of molded articles from the polycarbonates.
    [125] The invention therefore also relates to shaped articles obtainable from the thermoplastic polymer mixtures according to the invention, for example optical data storage media, preferably compact discs and DVDs.
    [126] The thermoplastic polymer mixtures according to the invention have the advantage that they have better thermal stability during the manufacture of the molded articles, and that the resulting final product (molded article) can be easily separated from the production mold and does not leave impurities on the mold.
    [127] The following examples are intended to illustrate the invention, but the invention is not limited to the examples.
    [128] Examples of Polycarbonates Prepared by Phase Interfacial Method
    [129] The following mixture was prepared:
    [130] According to the table below, with a BPA-PC having a terminal tert-butylphenol group, prepared by the phase interfacial method and having an average solution viscosity (measured in methylene chloride at a concentration of 0.5 g in 100 ml of methylene chloride at 25 ° C.) of 1.195 The amount of polycarbonate granules x wt% of the prepared polycarbonate granules was thoroughly mixed with the content of y wt% of glycerol monostearate and the z wt% of phosphorus compound in a closed container. The mixture was then compounded at an internal temperature of about 240 ° C. on a Berner Pfleiderer ZSK 53 type twin screw kneader.
    [131] (Furtherance)PolycarbonateGlycerol MonostearatePhosphite 1Phosphite 2 Example 199.9550.040.005Example 299.950.040.01Comparative Example 199.9550.04 0.005 Comparative Example 299.950.04 0.01 Comparative Example 3 (there is no stabilizer)99.960.0400
    [132] The product Loxiol EP 129 manufactured by Henke KgaA was used as glycerol monostearate. Phosphite 1 is (2,4,6-tri-tert-butyl-phenyl)-(2-butyl available from GE Specialty Chemicals under the tradename Ultranox 641®. 2-ethyl-propane-1,3-diyl) -phosphite. Phosphite 2 is Tris (2,4-di-tert-butylphenyl) phosphite, available from Ciba-Geigy as Irgafos 168.
    [133] In order to measure the product stability of the CD, a blank CD of the above-mentioned material was produced on a Net Injection Discjet 600 type CD injection molding machine. The CD had a thickness of 1.2 mm and an outer diameter of 120 mm. Product stability was tested under various mechanical conditions, indicated below in settings 1-4.
    [134] Setting 1:
    [135] Cylinder temperature (supply / compression / cylinder head / nozzle) 315/320/320/320 ° C .; Injection speed: 130 mm / sec; Mold (temperature before operation): 55 ° C .; Cycle time: 4.6 seconds
    [136] Setting 2:
    [137] Cylinder temperature (supply / compression / cylinder head / nozzle) 315/340/350/350 ° C .; Injection speed: 110 mm / sec; Mold (temperature before operation): 55 ° C .; Cycle time: 4.9 seconds
    [138] Setting 3:
    [139] Cylinder temperature (supply / compression / cylinder head / nozzle) 315/360/380/380 ° C .; Injection speed: 100 mm / sec; Mold (temperature before operation): 55 ° C .; Cycle time: 5.5 seconds
    [140] Setting 4:
    [141] Same as setting 2, except for stopping the machine for 5 minutes between cycles. After the injection molding machine was restarted each time, a fifth feed was taken and the following measurements were taken.
    [142] The remaining glycerol monostearate content and phenolic OH group content were then measured on the blank CD. The following results were obtained:
    [143] (GMS measurement—GMS concentration in ppm in CD under various conditions after preparation)Setting 1Setting 2Setting 3Setting 4 Example 1305285280255 Example 2355315300290 Comparative Example 1290270255195 Comparative Example 2320290265210 Comparative Example 3 (there is no heat stabilizer)285255205140
    [144] The concentration of phenolic OH in the CD was also measured under various conditions after preparation.
    [145] (Phenolic OH concentration in ppm in CD under various conditions after measurement-preparation of phenolic OH)Setting 1Setting 2Setting 3Setting 4 Example 1120130130140 Example 2105120125130 Comparative Example 1120135135150 Comparative Example 2120135140150 Comparative Example 3125145155175
    [146] (Coating test)Coating formation Example 1slightly Example 2slightly Comparative Example 1slightly Comparative Example 2middle Comparative Example 3A lot of
    [147] Coating formation was measured as follows: In order to measure the coating in the mold, a thousand partially filled blank CDs were prepared with Axxicon CD molds in each case on a Nestal Discjet 600 type CD injection molding machine. Approximately 80% partial filling of the CD was achieved by reducing the meteringpath and accepting following pressure. The cylinder temperature was 300 ° C. in the feed zone and 310 ° C. in the compression zone, with a temperature of 330 ° C. prevailing in the cylinder head and nozzle. The cycle time was about 5.5 seconds. After the 1000th shot, the surface of the die and the level of the outer area, ie the area not in contact with the polycarbonate melt, were visually observed for coating formation. The result was obtained.
    [148] Examples of Polycarbonates Prepared by Melt Transesterification Methods
    [149] Poly-BPA-PC with terminal phenol groups, prepared by the melt transesterification method and having an average solution viscosity (measured in methylene chloride at a concentration of 0.5 g in 100 ml of methylene chloride at 25 ° C.) of 1.200. The content of carbonate granules x wt% was thoroughly mixed with the content of y wt% of glycerol monostearate and the z wt% of phosphorus compounds in a closed container. The mixture was then compounded at an internal temperature of about 240 ° C. on a Berner Pladerer ZSK 53 type biaxial screw kneader.
    [150] (Furtherance)PolycarbonateGlycerol MonostearatePhosphite 1Phosphite 2 Example 199.060.030.01Comparative Example 199.060.03 0.01 Comparative Example 2 (there is no stabilizer)99.070.03
    [151] The product Roxyol EP 129 made by Henke was used as glycerol monostearate. Phosphite 1 is (2,4,6-tri-tert-butyl-phenyl)-(2-butyl-2-ethyl-propane-1 available from GE Specialty Chemicals under the tradename Ultra Knox 641 (R). , 3-diyl) -phosphite. Phosphite 2 is Tris (2,4-di-tert-butylphenyl) phosphite, available from Ciba-Geigy as Irgafos 168.
    [152] In order to measure the product stability of the CD, a blank CD made of the above-mentioned material was produced on a CD injection molding machine of the Netztal Discjet 600 type. The CD had a thickness of 1.2 mm and an outer diameter of 120 mm. Product stability was checked under machine setting 3 of the above machining program.
    [153] The remaining glycerol monostearate content was then measured on the blank CD. The following results were obtained:
    [154] (GMS measurement—GMS concentration in ppm in CD under various conditions after preparation)Setting 3 Example 1285 Comparative Example 1195 Comparative Example 2 (there is no heat stabilizer)180
    [155] (Coating test)Coating Formation (%) Example 10.049 Comparative Example 10.099 Comparative Example 20.160
    [156] Measurement of the amount of condensate
    [157] The amount of condensate was measured by weighing aluminum foil with and without coating. The amount of coating is defined as follows:
    [158] Amount (%) = the condensate (measured after the film - weight of the film before the measurement) / weight of sample x 100%
    [159] Detailed description of the method
    [160] After drying (120 ° C., 4 h), 20 g of granular material was poured into an aluminum dish having a diameter of 80 mm and a depth of 15 mm so that the bottom of the dish was uniformly covered with the granular material. This filled dish was introduced into a specially provided sample chamber (85 mm diameter, 50 mm depth) of electrically heatable metal blocks and covered with aluminum foil 100 mm in diameter and 0.03 mm thick. In order to allow the volatile components to condense on the foil, the foil was cooled with a cold plate during the measurement. The temperature of the cooling water was adjusted to 20 ° C. When making measurements, the foil must be able to seal the sample chamber well from the outside.
    [161] The metal block was heated to a temperature of 300 ° C. in a few minutes. The sample was continued at this temperature for 4 hours and then the test apparatus was cooled to ambient temperature. After reaching ambient temperature, the aluminum foil was removed and weighed on the micro-balance to calculate the amount of condensate according to the above definition.
    [162] Detailed description of the measurement method
    [163] Glycerol Monostearate
    [164] Glycerol monostearate was separated by gas chromatography on a capillary column and detected using a flame ionization detector. Evaluation was made by an internal standard method. The measurement limit was about 10 ppm.
    [165] Phenolic OH
    [166] The polycarbonate was dissolved in dichloromethane and reacted with titanium (IV) chloride to form an orange colored complex, the absorbance of which was measured photometrically at 546 nm. The calibration curve was prepared using BPA as an external standard. The measurement limit was about 20 ppm OH.
    权利要求:
    Claims (10)
    [1" claim-type="Currently amended] A thermoplastic polymer mixture containing at least one polycarbonate, at least one release agent and at least one phosphite having the formula:
    <Formula>

    In the above formula,
    n represents the number 0-5, preferably 1-3, and very preferably 3,
    Y independently of each other at each occurrence represents an alkyl or optionally substituted aryl, preferably C 1 -C 4 alkyl, particularly preferably methyl, sec-butyl and tert-butyl,
    m represents a number from 1 to 3, preferably 3, and
    X represents, in each case independently, an optionally substituted methylene radical, wherein at least one methylene radical must be completely substituted and the substituents are independently of each other a group comprising C 1 -C 20 alkyl, preferably C 1 -C Two substituents of a methylene radical selected from or completely substituted with 20 alkyl together represent the following radicals:

    R 1 is selected from the group comprising C 1 -C 18 alkyl, C 3 -C 12 cycloalkyl, C 6 -C 30 alkaryl and aryl, these radicals again being 1 to 4 O-alkylene-O and (Or) carboxylic ester-COO-radicals; C 2 -C 18 polyhydroxyalkyl containing 2 to 10 hydroxyl groups; It may be substituted by a C 2 -C 18 polyphenyl radical containing 2 to 10 phenolic OH groups.
    [2" claim-type="Currently amended] The thermoplastic polymer mixture of claim 1, wherein the release agent is an ester of a polyhydric alcohol having a long chain carboxylic acid, which ester contains at least one free OH group.
    [3" claim-type="Currently amended] The polymer mixture of claim 1, wherein the release agent is a partial ester of glycerol, trimethylol propane, pentaerythritol or similar polyhydric alcohols and saturated monovalent fatty acids containing 16 to 22 carbon atoms.
    [4" claim-type="Currently amended] 4. The polymer mixture of claim 1, wherein said polycarbonate has a molecular weight of 15,000 to 35,000.
    [5" claim-type="Currently amended] The polymer mixture according to any one of claims 1 to 4, containing 0.01 to 1.5% by weight of release agent and 0.001 to 0.1% by weight of phosphite.
    [6" claim-type="Currently amended] A method for producing a molded article, using the polymer mixture according to any one of claims 1 to 5.
    [7" claim-type="Currently amended] An optical data storage medium prepared from the thermoplastic polymer mixture of any one of claims 1 to 5.
    [8" claim-type="Currently amended] A method for producing a molded article, characterized by using a mixture according to any one of claims 1 to 5.
    [9" claim-type="Currently amended] Use of a mixture according to any one of claims 1 to 5 used to prepare thermoplastic polymers and shaped articles which can be prepared therefrom.
    [10" claim-type="Currently amended] Use of the polymer mixtures according to any one of claims 1 to 5 used to produce shaped articles.
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    同族专利:
    公开号 | 公开日
    JP2004526028A|2004-08-26|
    KR100839305B1|2008-06-17|
    WO2002077087A1|2002-10-03|
    DE10114803A1|2002-10-10|
    ES2305202T3|2008-11-01|
    CN1244619C|2006-03-08|
    AT397034T|2008-06-15|
    HK1068361A1|2006-10-20|
    US6899939B2|2005-05-31|
    US20020173566A1|2002-11-21|
    CN1516719A|2004-07-28|
    TWI310778B|2009-06-11|
    EP1379583A1|2004-01-14|
    JP4128874B2|2008-07-30|
    EP1379583B1|2008-05-28|
    DE50212321D1|2008-07-10|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-03-26|Priority to DE10114803.8
    2001-03-26|Priority to DE2001114803
    2002-03-13|Application filed by 바이엘 악티엔게젤샤프트
    2002-03-13|Priority to PCT/EP2002/002721
    2003-11-19|Publication of KR20030088470A
    2008-06-17|Application granted
    2008-06-17|Publication of KR100839305B1
    优先权:
    申请号 | 申请日 | 专利标题
    DE10114803.8|2001-03-26|
    DE2001114803|DE10114803A1|2001-03-26|2001-03-26|New polymer blends|
    PCT/EP2002/002721|WO2002077087A1|2001-03-26|2002-03-13|Novel polymer blends|
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