Thermoplastic polymer composition containing a stabilizer mixture

Abstract

The present invention relates to a composition comprising a) a thermoplastic polymer, preferably a polyolefin, and b) a stabilizer mixture comprising at least two components selected from (i), (ii), and (iii), wherein component (i) is a hydroxylamine or amine oxide; component (ii) is benzofuran-2-one of formula (I); and component (iii) is chromanol. [Formula 1] In formula JPEG2026515667000042.jpg38170, R3 is a substituted carbocyclic or heterocyclic aromatic ring system, and R4, R5, R6, and R7 are substituents selected from hydrogen or chloro; hydroxy; a substituted or unsubstituted hydrocarbyl group optionally containing at least one heteroatom; a substituted or unsubstituted hydrocarbyloxy group optionally containing at least one further heteroatom; a substituted or unsubstituted cyclohydrocarbyl group optionally containing at least one heteroatom; or a substituent optionally containing at least one further heteroatom. The composition is defined as follows: if the stabilizer mixture contains components (i) and (ii) and / or (iii), it is present in the composition in an amount less than 500 ppm by total weight of components (i) and (ii) and / or (iii) in the stabilizer mixture, based on the weight of the thermoplastic polymer; and if the stabilizer mixture contains components (ii) and (iii) without (i), it is present in the composition in an amount less than 300 ppm, preferably less than 250 ppm, preferably 200 ppm or less, more preferably 150 ppm or less, and even more preferably 100 ppm or less by weight of components (ii) and (iii), based on the weight of the thermoplastic polymer. A method for producing the composition, as well as the use of the stabilizer mixture and a particular stabilizer mixture, are also claimed.

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic polymer composition, preferably a polyolefin, comprising a stabilizer mixture. This thermoplastic composition can be processed, for example, in the production of molded articles, such as fibers or films, under conditions known to induce oxidative, thermal, or photo-induced degradation of the thermoplastic polymer. The thermoplastic polymer composition of the present invention has been found to provide effective processability with reduced degradation and / or good reduction of discoloration of the thermoplastic polymer. The present invention also relates to a method for producing such a thermoplastic composition and the use of a stabilizer mixture for this purpose. In addition, the present invention also includes specific stabilizer mixtures. [Background technology]

[0002] Various compounds have been used as processing stabilizers when processing thermoplastic polymers, with the aim of reducing the risk of inducing oxidative, thermal, or photo-induced degradation during processing.

[0003] The use of benzofuran-2-one type compounds as stabilizers for organic polymers is known, for example, from U.S. Patent Nos. 4,325,863; 4,388,244; 5,175,312; 5,252,643; 5,216,052; 5,369,159; 5,488,117; 5,356,966; 5,367,008; 5,428,162; 5,428,177; or 5,516,920.

[0004] In particular, sterically hindered amines, such as compounds containing a 2,2,6,6-tetramethylpiperidyl group, are known as "hindered amine" light stabilizers (HALS).

[0005] Polyolefin fibers have been stabilized with sterically hindered phenols combined with compounds from the group of organic phosphites or phosphonites, and sometimes with the additional use of light stabilizers.

[0006] U.S. Patent No. 6,521,681 reports that the use of such stabilizer mixtures may have the undesirable effect of yellowing of polyolefin fibers thus produced, particularly under the action of NOx gas, which is known in the art as gas fading. In many cases, discoloration occurs even during processing, especially in the case of melt extrusion. Compounds from the group of sterically hindered amines, which can be added as light stabilizers, are also known to exhibit antagonistic effects together with sterically hindered phenols, which adversely affect long-term thermal stability.

[0007] U.S. Patent No. 6,521,681 provides and describes a stabilizer mixture comprising at least one benzofuran-2-one type compound and at least one sterically hindered amine type compound, which is reported to be particularly suitable as a stabilizer for organic materials susceptible to oxidative, thermal, or photo-induced decomposition. These stabilizer systems are said to suppress discoloration of organic materials during processing, exhibit excellent resistance to the effects of NOx (no gas discoloration), and further demonstrate improved long-term thermal stability compared to stabilizer systems containing phenolic antioxidants.

[0008] Pamphlet PCT application number International Publication No. 99 / 03915 A1 discloses that blends of various lactones and phosphites provide better protection from polymer degradation during processing. This is said to be demonstrated by changes in melt flow and may provide better resistance to yellowing. Example 2 compares a trisnonylphenyl phosphite / lactone blend with nonyl-3-phenyl-3H-benzofuran-2-one and 5,7-di-t-butyl-3-phenyl-3H-benzofuran-2-one as lactones, the structures of which are illustrated on page 11. Example 3 compares phosphite / lactone blends with and without vitamin E. Specifically, blend #7 contained 75 wt% tris(nonylphenyl)phosphite, 15 wt% nonyl-3-phenyl-3H-benzofuran-2-one, and 10 wt% vitamin E and was used to process polypropylene at 1000 ppm.

[0009] U.S. Patent Application Publication No. 2006 / 0135792 A1 describes compounds, compositions, and methods for their synthesis related to the lactone antioxidant 3-arylbenzofuranone. This disclosure reveals that the compounds may be useful in preventing yellowing and degradation of organic materials, preferably polymers, such as polyurethane foams. The lactone antioxidant may be a polymer and may be a liquid or paste in physical form at room temperature. Furthermore, it has been shown that the compositions may have one or more reactive primary OH groups on a polar chain.

[0010] PCT application number International Publication No. 2015 / 121445 A1 and PCT application number International Publication No. 2017 / 025431 A1 describe compositions comprising an organic material to be stabilized and a specific group of phosphorus-containing 3-phenyl-benzofuran-2-one derivatives as stabilizers for the organic material. Such organic materials are susceptible to oxidative, thermal, or photo-induced decomposition. It is stated that these may be, for example, polymers, oligohydroxy compounds, waxes, fats, or mineral oils.

[0011] PCT application number International Publication No. 2016 / 020322 A1 and PCT application number International Publication No. 2019 / 243267 A1 define compositions comprising an organic material to be stabilized and a specific group of 3-phenyl-benzofuran-2-ondiphosphite or 3-phenyl-benzofuran-2-ondiphosphite derivatives as stabilizers. Such organic materials are susceptible to oxidative, thermal, or photo-induced decomposition. It is stated that these may be, for example, polymers, oligohydroxy compounds, waxes, fats, or mineral oils.

[0012] PCT application number International Publication No. 2019 / 010167 A1 brochure describes a polyolefin composition comprising a polyolefin, one or more phosphorus-containing benzofuranone compounds, and one or more hindered phenolic antioxidants which are said to provide excellent protection against discoloration during melt processing and enhanced thermal stability. Example 2 compares seven different additive mixtures for compounding with fiber-grade Ziegler-Natta polypropylene homopolymer (Zn-PP). Additive mixture #7 contains 375 ppm Phos1 (organophosphorus stabilizer, tris(2,4-di-tert-butylphenyl) phosphite); 500 ppm AO7 (alpha-tocopherol); and 125 ppm benzofuranone (109) (structural formula shown on page 20).

[0013] Chromanol compounds such as tocopherol have been used in formulations to stabilize plastic materials.

[0014] U.S. Patent No. 4,806,580 describes a stabilizer mixture for stabilizing plastics, such as polypropylene, during processing. The stabilizer mixture contains (a) a chroman derivative and (b) an organic phosphite or phosphonite in a weight ratio of a:b of 1:5 to 1:14.

[0015] European Patent Application No. 542108 A2 discloses a stabilizing mixture for polyethylene-containing plastics comprising (a) a tocopherol compound and (b) a phosphorus or sulfur-containing secondary antioxidant in a weight ratio of 1:1.4 to 1:5 a:b. A corresponding disclosure is found in the paper by SFLaermer and PFZambetti, published in the Journal of Plastic Film & Sheeting, volume 8, 1992, pages 228-248. This paper further describes a mixture of alpha-tocopherol and phosphite in a weight ratio of 1:1:4 for the stabilization of polypropylene.

[0016] The paper by SSYoung, SFLaermer, and PFZambetti, published in the Journal of Plastic Film and Sheeting, volume 11, 1995, pages 126-142, demonstrates that alpha-tocopherol formulations can replace phenol / phosphite combinations as primary antioxidant systems, or that alpha-tocopherol formulations can actually replace the phosphite portion to achieve better performance.

[0017] N,N-dialkylhydroxylamines are known to be useful processing stabilizers for polyolefins such as polypropylene.

[0018] U.S. Patent No. 4,590,231 describes a composition stabilized against degradation, comprising (a) a saturated polyolefin or a mixture thereof; (b) a stabilizing amount of a stabilizer or a mixture of stabilizers selected from the group consisting of phenolic antioxidants, hindered amine light stabilizers, ultraviolet light absorbers, organophosphorus compounds, alkali metal salts of fatty acids, and thio synergists; and (c) a stabilizing amount of a hydroxylamine derivative or a mixture thereof.

[0019] Chinese Patent Application Publication No. 115819842A claims a hindered phenyl-containing anti-coloring antioxidant composition for polymers, characterized in that it comprises the following components: (1) a primary antioxidant, (2) a secondary antioxidant, (3) a carbon-free base scavenger, (4) a color-blocking agent, and (5) a catalyst. Example 5 describes providing 100 parts of polypropylene powder, 0.5 parts of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentaerythritol ester, 0.3 parts of tris(2,4-di-tert-butylphenyl)phosphate ester, 0.06 parts of N,N-bis(octadecyl)hydroxylamine, 0.06 parts of 5,7-di-tert-butyl-3-(3,4-dimethyl)benzofuran-2(3H)-one, 0.1 parts of butan-1,4-(3-(4-mercaptophenyl)propionate) and 0.05 parts of tris(pentafluorophenyl)borane, which are uniformly mixed by a high-speed mixer and then extruded by a twin-screw extruder. The extruder is used to extrude at temperatures in each zone from 200 to 240°C, and then a pelletizer is used for traction and pelletization to obtain modified polypropylene pellets.

[0020] Japanese Patent Publication No. 2008-230079 addresses the problem of providing a laminate made from a non-halogen resin with excellent weather resistance, heat resistance, and discoloration resistance. This reference specifies a solution for providing a laminate made of a non-halogen resin in which the outermost surface is covered with a sheet made of a non-halogen resin containing 0.05 to 3.0 parts by weight of a light stabilizer and 0.01 to 2.0 parts by weight of an antioxidant based on 100 parts by weight of the non-halogen resin. Table 2, Sample 3 describes using 80 parts of an olefin-type thermoplastic elastomer and 20 parts of random polypropylene as the resin. The additives include 0.07 parts of the antioxidant hydroxylamine Irgastab FS 042, 0.07 parts of the antioxidant lactone-based HP-136, 0.05 parts of the optical stabilizer Chimassorb 944 (an N-hydrogen-substituted hindered amine type), several parts of the filler calcium carbonate, and 0.1 parts of the lubricant zinc stearate.

[0021] U.S. Patent No. 5,834,541 relates to a polymer composition comprising (i) an olefin polymer containing an acid neutralizer other than a metal salt of a saturated or unsaturated fatty acid, and (ii) a stabilizer system distributed throughout the polymer, wherein the stabilizer system comprises (a) a phosphite selected from the group consisting of 2,2',2''-nitrilo[triethyl-tris(3,3',5,5'-tetra-tert-butyl-1,1-diphenyl-2,2'-diyl)phosphite] and tris(2,4-di-tert-butylphenyl)phosphite; and (b) an N,N-dialkylhydroxylamine, benzofuranone, or a mixture thereof. This patent demonstrates that smoke generation during fiber, film, and sheet processing can be significantly reduced by (1) a combination of N,N-dialkylhydroxylamine and a specific phosphite stabilizer for melt stabilizing a controlled rheological olefin polymer, and (2) an acid neutralizer other than a metal salt of a saturated or unsaturated fatty acid.

[0022] The paper by S Al-Malaika et al., entitled "Stabilisation of metallocene ethylene-1-octene copolymers during multiple extrusions," Polymer Degradation and Stability 93(2008)1619-1631, refers to the melt stabilization efficiency of antioxidants with different structures based on hindered phenols, phosphite esters, phosphonites, and lactones, which were tested during multiple extrusions at 265°C in three metallocene ethylene-1-octene copolymers (m-LLDPE) with different degrees of short-chain branching (SCB) and one Zigler copolymer (z-LLDPE) containing the same level of SCB corresponding to one m-LLDPE polymer. Table 4 exemplifies antioxidant mixtures used in the formulation of m-LLDPE and z-LLDPE polymers. One of the antioxidant mixtures listed is Irganox E201:Ultranox 626:HP 136, at concentrations of 300 ppm:600 ppm:250 ppm, respectively.

[0023] European Patent Application No. 323409 A2 describes a stabilized polyolefin composition having a long-chain N,N-dialkylhydroxylamine. The two alkyl groups are said to be independently alkyl groups with 12 to 18 carbon atoms. Hydroxylamines derived from di(hydrogenated fat)amines are said to be particularly useful for this purpose. The polyolefin is said to be preferably a homopolymer of alphaolefins. Saturated polyolefins include polymers derived from monoolefins that can be crosslinked, such as polyethylene, polypropylene, polyisobutylene, polybutene-1, poly-3-methylbutene-1, and poly-4-methylpentene-1.

[0024] PCT application number International Publication No. 00 / 12605 relates to a high melt-flow polypropylene composition that provides a reduction in shape defects when extruded into fibers or films. The composition is said to comprise a high melt-flow polypropylene resin, a stabilized amount of N,N-dialkylhydroxylamine, a stabilized amount of an organic phosphite or phosphonite, and optionally other conventional additives such as antioxidants, acid acceptors, light stabilizers, ultraviolet absorbers, etc.

[0025] U.S. Patent No. 6,872,764, B2 describes an improved strength and / or discoloration-resistant polyolefin article that is essentially free of phenol antioxidants and incorporates a stabilization system sufficient to mitigate the harmful effects of gamma irradiation. The stabilization system comprises (a) one or more hindered amine stabilizers, (b) one or more compounds selected from the group consisting of i) hydroxylamine stabilizers, ii) nitro stabilizers, iii) amine oxide stabilizers, and iv) benzofuranone stabilizers; and optionally (c) one or more compounds selected from the group consisting of organic phosphites and phosphonites. The article is said to be subjected to one or more doses of gamma irradiation.

[0026] European Patent Application No. 867467 A1 relates to a thermoplastic resin composition comprising a thermoplastic resin or a mixture thereof and a stabilizing amount of a stabilizer or a mixture of stabilizers. The stabilizer or mixture of stabilizers is selected from the group consisting of phenolic antioxidants, 3-arylbenzofuranones, hindered amine stabilizers, ultraviolet absorbers, organophosphorus compounds, alkali metal salts of fatty acids, hydroxylamines, and thio synergists, and a stabilizing amount of tertiary amine oxides. The composition is said to have improved stability against discoloration when exposed to heating or combustion products of natural gas due to the simultaneous presence of an effective amount of tertiary amine oxide.

[0027] N,N-dialkylhydroxylamine is effective as both a primary antioxidant (hydrogen donor) and a secondary antioxidant (peroxide scavenger), and therefore can be effectively used in phenol-free processing stabilizer systems. Processing stabilizer systems containing N,N-dialkylhydroxylamine are very effective as processing stabilizers for various thermoplastics, typically polyolefins. Nevertheless, hydroxylamine has been found to be less effective at temperatures above 230°C, for example, above 250°C. This may be a disadvantage for processing thermoplastics such as polypropylene fiber processing, where temperatures above 230°C or above 250°C can be used, for example, as high as 280-300°C, which can be used in fiber spinning to achieve high throughput. [Overview of the project] [Problems that the invention aims to solve]

[0028] The object of the present invention is to provide a stabilizer system for processing thermoplastic plastics, such as polyolefins, such as polypropylene, that can be used in high-temperature processing, for example at a temperature of at least 230°C, and that provides a good balance of performance characteristics. A further object is to find a stabilizer system that achieves good color stability and / or processing characteristics in the processing of thermoplastic plastics. Furthermore, it would be desirable that such a stabilizer system does not contain phenol or has a reduced phenol content. For the purposes of the present invention, chromanol is not a phenol. [Means for solving the problem]

[0029] It has been found that a combination of at least two components selected from (i) hydroxylamine or amine oxide; (ii) a specific benzofuran-2-one, typically based on a 3-arylbenzofuran-2-one derivative; and (iii) chromanol can provide an effective stabilizer mixture for processing thermoplastics such as polyolefins, exhibiting good processing characteristics and providing reduced degradation and / or color yield of the thermoplastic polymer.

[0030] A first aspect of the present invention is: a) Thermoplastic polymers, preferably polyolefins; b) A stabilizer mixture comprising at least two components selected from (i), (ii), and (iii) A composition comprising, During the ceremony, Component (i) is a hydroxylamine or amine oxide; Component (ii) is benzofuran-2-one of formula (I); Component (iii) is chromanol, [ka] During the ceremony, R3 is a substituted carbocyclic or heterocyclic aromatic ring system. R4, R5, R6, and R7 are each independently of each other a substituent selected from hydrogen or chloro; hydroxy; a substituted or unsubstituted hydrocarbyl group optionally containing at least one heteroatom; a substituted or unsubstituted hydrocarbyloxy group optionally containing at least one further heteroatom; a substituted or unsubstituted cyclohydrocarbyl group optionally containing at least one heteroatom; or a hydrocarbylthio group optionally containing at least one further heteroatom. If the stabilizer mixture contains components (i), (ii), and / or (iii), then it is present in the composition in an amount less than 500 ppm by total weight of components (i), (ii), and / or (iii) present in the stabilizer mixture, based on the weight of the thermoplastic polymer. If the stabilizer mixture contains components (ii) and (iii) without (i), it is present in the composition in an amount of less than 300 ppm, preferably less than 250 ppm, preferably 200 ppm or less, more preferably 150 ppm or less, and even more preferably 100 ppm or less, based on the weight of the thermoplastic polymer. The composition is defined.

[0031] A second aspect of the present invention is: A method for preparing the composition comprising the step of processing a thermoplastic polymer, preferably a polyolefin, in the presence of a stabilizer mixture, wherein the stabilizer mixture is incorporated into the thermoplastic polymer or applied to the thermoplastic polymer before or during processing of the thermoplastic polymer. The stabilizer mixture comprises at least two components selected from (i), (ii), and (iii), During the ceremony, Component (i) is a hydroxylamine or amine oxide; Component (ii) is benzofuran-2-one of formula (I); Component (iii) is chromanol, [ka] During the ceremony, R3 is a substituted carbocyclic or heterocyclic aromatic ring system. R4, R5, R6, and R7 are each independently of each other a substituent selected from hydrogen or chloro; hydroxy; a substituted or unsubstituted hydrocarbyl group optionally containing at least one heteroatom; a substituted or unsubstituted hydrocarbyloxy group optionally containing at least one further heteroatom; a substituted or unsubstituted cyclohydrocarbyl group optionally containing at least one heteroatom; or a hydrocarbylthio group optionally containing at least one further heteroatom. If the stabilizer mixture contains components (i), (ii), and / or (iii), then it is present in the composition in an amount less than 500 ppm by total weight of components (i), (ii), and / or (iii) present in the stabilizer mixture, based on the weight of the thermoplastic polymer. If the stabilizer mixture contains components (ii) and (iii) without (i), it is present in the composition in an amount of less than 300 ppm, preferably less than 250 ppm, preferably 200 ppm or less, more preferably 150 ppm or less, and even more preferably 100 ppm or less, based on the weight of the thermoplastic polymer. Provide a method.

[0032] A third aspect of the present invention is the use of a stabilizer mixture to improve processability and / or reduction of discoloration when processing thermoplastic polymers, preferably polyolefins, During the ceremony, The stabilizer mixture comprises at least two components selected from (i), (ii), and (iii), During the ceremony, Component (i) is a hydroxylamine or amine oxide; Component (ii) is benzofuran-2-one of formula (I); Component (iii) is chromanol, [ka] During the ceremony, R3 is a substituted carbocyclic or heterocyclic aromatic ring system. R4, R5, R6, and R7 are substituents independently selected from hydrogen or chloro; hydroxy; a substituted or unsubstituted hydrocarbyl group optionally containing at least one heteroatom; a substituted or unsubstituted hydrocarbyloxy group optionally containing at least one further heteroatom; a substituted or unsubstituted cyclohydrocarbyl group optionally containing at least one heteroatom; or a hydrocarbylthio group optionally containing at least one further heteroatom. If the stabilizer mixture contains components (i), (ii), and / or (iii), then it is present in the composition in an amount less than 500 ppm by total weight of components (i), (ii), and / or (iii) present in the stabilizer mixture, based on the weight of the thermoplastic polymer. If the stabilizer mixture contains components (ii) and (iii) without (i), it is used in an amount of less than 300 ppm, preferably less than 250 ppm, preferably 200 ppm or less, more preferably 150 ppm or less, and even more preferably 100 ppm or less, based on the weight of the thermoplastic polymer, by the weight of components (ii) and (iii). Provides usage.

[0033] A fourth aspect of the present invention is a stabilizer mixture for processing thermoplastic polymers, preferably polyolefins, wherein the composition comprises component (i) and component (iii) and optionally component (ii), During the ceremony, Component (i) is a hydroxylamine or amine oxide; Component (ii) is benzofuran-2-one of formula (I); Component (iii) is chromanol, [ka] During the ceremony, R3 is a substituted carbocyclic or heterocyclic aromatic ring system. The present invention provides a stabilizer mixture in which R4, R5, R6, and R7 are substituents independently selected from hydrogen or chloro; hydroxy; a substituted or unsubstituted hydrocarbyl group optionally containing at least one heteroatom; a substituted or unsubstituted hydrocarbyloxy group optionally containing at least one further heteroatom; a substituted or unsubstituted cyclohydrocarbyl group optionally containing at least one heteroatom; and a hydrocarbylthio substituent optionally containing at least one further heteroatom. [Modes for carrying out the invention]

[0034] According to various aspects of the present invention, the stabilizer mixture is I) (i) a mixture of a hydroxylamine or amine oxide and (ii) a benzofuran-2-one of formula (I); II) A mixture of (i) hydroxylamine or amine oxide and (iii) chromanol; III)(ii) A mixture of benzofuran-2-one of formula (I) and (iii) chromanol; or IV) A mixture of (i) a hydroxylamine or amine oxide, (ii) benzofuran-2-one of formula (I), and (iii) chromanol. It is possible.

[0035] Component (i) of the stabilizer mixture should preferably be a substituted hydroxylamine in which one or preferably two substituted or unsubstituted hydrocarbyl groups are bonded to the nitrogen of the hydroxylamine moiety. In one preferred embodiment, component (i) is of formula (II): [ka] (wherein R1 and R2 are each independently selected from optionally substituted alkyl, cycloalkyl, arylaralkyl, and alkaryl groups) is a hydroxylamine. In a preferred embodiment, R1 and R2 are each independently selected from C1 to C 30 Alkyl, C7-C9 phenylalkyl, unsubstituted or C1-C4 alkyl-substituted phenyl, unsubstituted or C1-C4 alkyl-substituted C5-C8 cycloalkyl, C1-C 18 It is an alkoxy. In a preferred embodiment, R1 and R2 are each independently C8-C 30 Alkyl alkyl group, preferably C 12 ~C 30 Alkyl alkyl groups, more C 16 ~C 20It is selected from an alkyl group. Even more preferably, R1 and R2 are independently an alkyl of 16 to 18 carbon atoms or a mixture thereof. Particularly interesting hydroxylamines include N,N-dioctadecylhydroxylamine and N,N-dihexadecylhydroxylamine or mixtures thereof. In a particularly preferred embodiment, the hydroxylamine is bis(hydrogenated palm oil alkyl)hydroxylamine. In another particularly preferred embodiment, the hydroxylamine is bis(hydrogenated tallow alkyl)amine oxide.

[0036] In an alternative embodiment, component (i) of the stabilizer mixture may be a substituted amine oxide in which one, two or preferably three substituted or unsubstituted hydrocarbyl groups are bonded to the nitrogen of the amine oxide. Desirably, the amine oxide is a tertiary amine oxide. In a desired embodiment, component (i) is of formula (III):

Chemical formula

[0037] In a preferred embodiment, R8 and R9 are each independently selected from a C8-C 30 alkyl group, preferably a C 12 -C 30 alkyl group, more preferably a C 12 -C 24 alkyl group, and R 9’is a methyl group. More preferably, R8 and R9 are each independently C 14 ~C 24 It is an alkyl group, R 9’ It is a methyl group.

[0038] Suitable amine oxides include dioctylmethylamine oxide, trioctylamine oxide, didecylmethylamine oxide, di(cocoalkyl)methylamine oxide, tri(cocoalkyl)amine oxide, di(fat alkyl)methylamine oxide, tri(fat alkyl)amine oxide, and tri(C 14 ~C 24 Alkyl amine oxide, di(C) 14 ~C 24 The tertiary amine oxide is selected from the group consisting of alkyl)methylamine oxide and mixtures containing any of the above. A preferred amine oxide is Genox® EP stabilizer, which is commercially available, for example, from SI Group, and has the chemical name amine, bis(hydrogenated rapeseed alkyl)methyl, N-oxide.

[0039] Amine oxides are known to undergo thermal elimination and high temperatures, such as 150°C to 200°C. Under such conditions, amine oxides can eliminate hydroxylamine, yielding an alkene. Therefore, there is a relationship between amine oxides and hydroxylamine, as such amine oxides may eliminate hydroxylamine in situ under the elevated conditions of thermoplastic polymer processing.

[0040] In a preferred embodiment, component (ii) of the stabilizer mixture is formula (IV): [ka] [In the formula, R4, R5, R6, and R7 are each independently of each other a substituent selected from hydrogen or chloro; hydroxy; optionally containing at least one heteroatom; optionally containing at least one further heteroatom; optionally containing at least one further heteroatom; optionally containing at least one further heteroatom; or optionally containing at least one further heteroatom; preferably, R4, R5, R6, and R7 are each independently of each other hydrogen or a C1-C8 alkyl group; R 10 , R 11 , R 12 , R 13 and R 14 These are, independently of each other, hydrogen, hydroxyl, and C1-C 12 Alkyl, -OR 15 , -NR 34 R 35 or substituents having one or repeating alkylene oxide units, where R 10 , R 11 , R 12 , R 13 and R 14 At least one of them is not hydrogen, R 10 , R 11 , R 12 , R 13 and R 14 The only one is -OR 15 or -NR 34 R 35 And, (R 15 (is a base of formula (V), or a base of formula (VA), or a base of formula (VI), or a base of formula (VI-A)) R 34 is the basis of equation (VI-A), R 35 is hydrogen or C1-C8 alkyl, [ka] A is C2~C 20 Containing an alkylene group or a divalent oligomeric oxyalkylene group, Z is C2~C 20 Containing alkyl or divalent oligomeric ester groups, G is a terminal group, consisting of hydrogen, C1-C 10 Selected from the group consisting of alkyl, alkylcarbonyl, and arylcarbonyl, R 16 This is either substituted or non-substituted C1~C 12 Alkyl groups; substituted or unsubstituted C4-C8 cycloalkyl groups; substituted or unsubstituted C5-C6 aryl groups, preferably substituted or unsubstituted phenyl groups, preferably R 16 C1~C 12 Alkyl or substituted phenyl group, more preferably R 16 This is a C1-C4 alkyl group or a substituted phenyl group having a hydroxyl group and one or two C1-C4 alkyl groups as substituents; Y is either oxygen or a covalent bond; If Y is oxygen, R 17 and R 18 These are, independently, equation (VI-A): [ka] (Each R 19 The group or groups are C1-C8 alkyl groups, independently of each other; m is an integer between 0 and 4; R 4’ , R 5’ , R 6’ and R 7’ (Each of these terms independently has the same meaning as R4, R5, R6, and R7.) Is it the basis of; or R 17 and R 18 Each of these elements is independent of the others and is either unsubstituted or C1-C8 alkyl, C 10 ~C8 alkoxy, halogen or one phenyl, C6~C 10 Aryl; C1~C 18 Alkyl; C3~C 16 Cycloalkyl; C7~C 13Arylalkyl; C2 - C 18 Alkenyl; C2 - C interrupted by one or more oxygen atoms 30 Alkyl; or C2 - C interrupted by one sulfur atom 16 is alkyl; or R 17 is, together with R 18 one of the structures of formula (VI - B), (VI - C) or (VI - D):

Chemical formula

[0041] In one embodiment of the benzofuran-2-one of formula IV, R4, R5, R6, and R7 are each independently of each other: hydrogen, chloro, hydroxy, and C1-C 25 Alkyl, C7-C9 phenylalkyl, unsubstituted or C1-C4 alkyl-substituted phenyl, unsubstituted or C1-C4 alkyl-substituted C5-C8 cycloalkyl; C1-C 18 Alkoxy, C1-C 18 Alkylthio, C1-C4 alkylamino, di-(C1-C4 alkyl)amino, C1-C 25 Alkanoyloxy, C1~C 25 Alkanoylamino, C3~C 25 Alkenoyloxy, oxygen, sulfur, or >NR 25 C3~C is interrupted by 25 It is an alkanoyloxy; R4, R5, R6, and R6 are also C6-C9 cycloalkylcarbonyloxy, benzoyloxy, or C1-C 12 It may be an alkyl-substituted benzoyloxy; or the substituents R4 and R5 or R5 and R6 or R6 and R7, together with the linked carbon atoms, form a benzene ring; or if R5 and R7 are hydrogen, R6 may further be a compound of formula (IV-A) [ka] And, During the ceremony, R 3’は , unsubstituted or C1-C4 alkyl or hydroxysubstituted phenylene or naphthalene; or -R 29 -XR 30 -and, R 4’’ These are hydrogen, chloro, hydroxy, C1-C 25 Alkyl, C6~C 10It is an aryl, phenyl, unsubstituted or C1-C4 alkyl-substituted phenyl, unsubstituted or C1-C4 alkyl-substituted C5-C8 cycloalkyl; C1-C 18 Alkoxy, C1-C 18 Alkylthio, C1-C4 alkylamino, di-(C1-C4 alkyl)amino, C1-C 25 Alkanoyloxy, C1~C 25 Alkanoylamino, C3~C 25 Alkenoyloxy, oxygen, sulfur, or >NR 31 C3~C is interrupted by 25 Alkanoyloxy; C6-C9 cycloalkylcarbonyloxy, benzoyloxy or C1-C 12 It is an alkyl-substituted benzoyloxy, R 10 , R 11 , R 12 , R 13 and R 14 It has the same definition as above, R 25 is hydrogen or a C1-C8 alkyl group; R 27 and R 28 These are, independently of each other, hydrogen, CF3, and C1~C 12 It is alkyl or phenyl, or R 27 and R 28 Together with linked carbon atoms, they form a C5-C8 cycloalkyl ring that is either unsubstituted or substituted with 1-3 C1-C4 alkyl groups. R 29 and R 30 Each of these is independently of the others, being other substituted or C1-C4 alkyl-substituted phenylene or naphthalene. R 31 is hydrogen or a C1-C8 alkyl group; R 32 is hydrogen or a C1-C8 alkyl group; X is a direct bond, oxygen, sulfur, or NR 32 That is the case.

[0042] C1-C8 alkyl groups are linear or branched, and examples include methyl, ethyl, n-propyl, 1-methyl-ethyl, n-butyl, 1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl-ethyl, n-pentyl, 1-methyl-butyl, 3-methyl-butyl, n-hexyl, 1-methyl-pentyl, 2-methyl-pentyl, 4-methyl-pentyl, 2-ethyl-butyl, n-heptyl, 1-methylhexyl, n-octyl, 1-methylheptyl, 2-ethylhexyl, 5,5-dimethylhexyl, or 1,1,3,3-tetramethyl-butyl. C1-C4 alkyl groups or C8 alkyl groups, particularly methyl, ethyl, 1-methyl-ethyl, 1-methyl-propyl, 1,1-dimethyl-ethyl, or 1,1,3,3-tetramethyl-butyl are preferred. C1-C4 alkyl groups, particularly methyl, ethyl, 1-methyl-ethyl, 1-methyl-propyl, 1,1-dimethyl-ethyl, and especially methyl, 1-methyl-propyl, or 1,1-dimethyl-ethyl are preferred.

[0043] C1~C 12 Alkyls are linear or branched, and include, for example, methyl, ethyl, n-propyl, 1-methyl-ethyl, n-butyl, 1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl-ethyl, n-pentyl, 1-methyl-butyl, 3-methyl-butyl, n-hexyl, 1-methyl-pentyl, 2-methyl-pentyl, 4-methyl-pentyl, 2-ethyl-butyl, n-heptyl, 1-methylhexyl, n-octyl, 1-methylheptyl, 2-ethylhexyl, 5,5-dimethylhexyl, 1,1,3,3-tetramethyl-butyl, n-nonyl, 2-ethyl-heptyl, n-decyl, undecyl, and n-dodecyl.

[0044] Unsubstituted or substituted with C1-C8 alkyl, C1-C8 alkoxy, halogen or one phenyl, C6-C 10Aryls include, for example, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 3,5-dimethylphenyl, 4-(1,1-dimethylethyl)phenyl, 4-(1,1,3,3-tetramethylpentyl)phenyl, naphthalen-1-yl, naphthalen-2-yl, 6-methylnaphthalen-2-yl, 4-phenylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 3-(n-propoxy)phenyl, 4-(1,1-dimethylethoxy)phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, and 2-chloro-4-methylphenyl. They are either unsubstituted or substituted with C1-C8 alkyl or C1-C8 alkoxy compounds, C6-C 10 - Aryls are preferred. Unsubstituted or substituted phenyls with C1-C8 alkyl groups are particularly preferred. Phenyls are especially preferred.

[0045] C1-C8 alkoxys are linear or branched, and examples include methoxy, ethoxy, n-propoxy, 1-methyl-ethoxy, n-butoxy, 1-methyl-propoxy, 1,1-dimethyl-ethoxy, n-pentoxy, 2-methyl-pentoxy, 2-ethyl-butoxy, 1-methyl-hexoxy, n-octoxy, 1-methyl-heptoxy, 2-ethyl-hexoxy, and 1,1,3,3-tetramethyl-butoxy. C1-C4 alkoxys, particularly methoxy, are preferred.

[0046] Halogens include, for example, fluorine atoms (=fluoro), chlorine atoms (=chloro), bromine atoms (=bromo), or iodine atoms (=iod). Chlorine atoms or fluorine atoms, with fluorine atoms being particularly preferred.

[0047] C1~C 18The alkyl is linear or branched, for example, methyl, ethyl, n-propyl, 1-methyl-ethyl, n-butyl, 1-methyl-propyl, 2-methyl-propyl, 1,1-dimethyl-ethyl, n-pentyl, 1-methyl-butyl, 3-methyl-butyl, n-hexyl, 1-methyl-pentyl, 2-methyl-pentyl, 4-methyl-pentyl, 2-ethyl-butyl, n-heptyl, 1-methyl-hexyl, n-octyl, 1-methyl-heptyl, 2-ethyl-hexyl, 5,5-dimethyl-hexyl, 1,1,3,3-tetramethyl-butyl, n-nonyl, 2-ethyl-heptyl, n-decyl, undecyl, n-dodecyl, tridecyl, tetradecyl, pentadecyl, n-hexadecyl or n-octadecyl. C1-C 18 alkyl, especially C1-C 12 alkyl is preferred.

[0048] C3-C 16 The C3-C7-cycloalkyl is unsubstituted or substituted by C1-C4 alkyl, for example, cyclobutyl, cyclopentyl, 3,4-dimethyl-cyclopentyl, cyclohexyl, 4-methyl-cyclohexyl, 4-(1-methylethyl)-cyclohexyl, 4-(1,1-dimethylethyl)-cyclohexyl, 3,5-dimethyl-cyclohexyl, 5-methyl-2-(1-methyl-ethyl)-cyclohexyl, cycloheptyl, cyclooctyl or cyclododecyl. C5-C7-cycloalkyl, especially cyclohexyl, is preferred.

[0049] C7-C 13 The aralkyl is, for example, benzyl, 4-methyl-benzyl, 2-phenyl-ethyl, 3,5-dimethyl-benzyl, 1-phenyl-1,1-dimethylmethyl, 3-phenyl-propyl, 3-phenyl-2-methyl-propyl, 3,5-di-tert-butyl-benzyl or 4-phenyl-phenyl-methyl. Benzyl is preferred.

[0050] C2-C 18The alkenyl is linear or branched, such as vinyl, allyl, Z- or E-but-2-enyl, Z- or E-but-3-enyl, Z- or E-pent-2-enyl, pent-4-enyl, Z- or E-2-methyl-but-2-enyl, Z- or E-3-methyl-but-3-enyl, Z- or E-hex-1-enyl, Z- or E-hexadec-9-enyl or E-octadec-9-enyl, (9Z,12Z)-octadeca-9,12-dienyl or (9Z,12Z,15Z)-octadeca-9,12,15-trienyl. Allyl is preferred.

[0051] Interrupted by one or more oxygen atoms, C2-C 30 The alkyl is linear or branched, such as methoxy-methyl, 2-methoxy-ethyl, 2-ethoxy-ethyl, 2-(2-methoxy-ethoxy)-ethyl, 2-n-butoxy-ethyl, 2-[2-(2-methoxy-ethoxy)-ethoxy]-ethyl, 2-[2-[2-(2-methoxy-ethoxy)-ethoxy]-ethoxy]-ethyl, 2-(2-methoxy-1-methyl-ethoxy)-1-methyl-ethyl, 3-(n-propoxy)-propyl, 2-[2-[2-(2-n-butoxy-ethoxy)-ethoxy]-ethoxy]-ethyl, 2-[2-(2-n-butoxy-2-methyl-ethoxy)-2-methyl-ethoxy]-2-methyl-ethyl or 2-[(2-n-lauryl)-ethoxy]-ethyl. 2-methoxy-ethyl or 2-ethoxy-ethyl is preferred.

[0052] Interrupted by one sulfur atom, C2-C 16 The alkyl is linear or branched, such as 2-(methyl-sulfanyl)-ethyl, 3-thiaundecyl or 3-thiapentadecyl.

[0053] In a preferred embodiment, in the formula (IV) benzofuran-2-one, R4 is hydrogen or C1-C8 alkyl, preferably C1-C4 alkyl, more preferably tertiary butyl, Both R5 and R7 are hydrogen, R6 is the base of equation (IV-A), R 10 , R 11 , R 12 , R 13 and R 14 Each of them is independently of the others, hydrogen or C1-C8 alkyl, preferably hydrogen or C1-C4 alkyl, more preferably methyl, where R 10 , R 11 , R 12 , R13 and R 14 At least one of them is a C1-C8 alkyl group, preferably R 10 , R 11 , R 12 , R 13 and R 14 One or two of them are C1-C4 alkyl, more preferably methyl. R 27 and R 28 Together with linked carbon atoms, they form a C6 cycloalkyl ring, preferably a cyclohexyl ring. R 3’ is equation (IV-B) [ka] (In the formula, R 33 This is a C1-C8 alkyl group, preferably a C1-C4 alkyl group, more preferably a methyl group. n is an integer between 1 and 5, preferably 1 or 2, more preferably 2. It is a substituted phenyl group, R 4’’ The C1-C8 alkyl group is preferably a C1-C4 alkyl group, and more preferably a tertiary butyl group.

[0054] In the benzofuran-2-one of another embodiment (IV), R4, R5, R6, and R7 are each independently hydrogen or a C1-C8 alkyl group; R 10 , R 11 , R 12 , R 13 and R 14 These are, independently of each other, hydrogen, hydroxyl, and C1-C12 Alkyl or -NR 34 R 35 And, Here, R 10 , R 11 , R 12 , R 13 and R 14 At least one of them is not hydrogen, R 10 , R 11 , R 12 , R 13 and R 14 The only one is -NR 34 R 35 And, Here, R 34 is the basis of equation (VI-A), R 35 is hydrogen or C1-C8 alkyl, Each R 19 The group or groups are C1-C8 alkyl groups, independently of each other; m is an integer between 0 and 4; R 4’ , R 5’ , R 6’ and R 7’ Each of these terms independently has the same meaning as R4, R5, R6, and R7.

[0055] Preferably, in embodiments of the benzofuran-2-one of formula (IV), R4, R5, R6, R7, R 4’ , R 5’ , R 6’ and R 7’ Each of these is independently hydrogen or a C1-C4 alkyl group, preferably hydrogen or a tertiary butyl group, and more preferably R4, R6, R 5’ and R 7’ It is a tertiary butyl, R5, R7, R 4’ and R 6’ is hydrogen; R 10 , R 11 , R 12 , R 13 and R 14 One of them is -NR 34 R 35 And R 10 , R 11, R 12 , R 13 and R 14 The remainder is hydrogen or a C1-C4 alkyl group, preferably R 12 -NR 34 R 35 And R 10 , or R 11 , R 13 and R 14 is hydrogen; R 34 is the basis of equation (VI-A), R 35 This is hydrogen or a C1-C4 alkyl group, preferably methyl. m is 0, Preferably, the bond of the group of formula (IV-A) to phenyl is at the para position.

[0056] In the benzofuran-2-one of further embodiment (IV), R4, R5, R6, and R7 are each independently of each other, hydrogen or a C1-C8 alkyl group; R 10 , R 11 , R 12 , R 13 and R 14 These are, independently of each other, hydrogen, hydroxyl, and C1-C 12 Alkyl or -OR 15 And, Here, R 10 , R 11 , R 12 , R 13 and R 14 At least one of them is not hydrogen, R 10 , R 11 , R 12 , R 13 and R 14 Only one of them is -OR 15 And, Here, R 15 is the basis of equation (VI-A), Each R 19 The group or groups are C1-C8 alkyl groups, independently of each other; m is an integer between 0 and 4; R 4’ , R5’ , R 6’ and R 7’ Each of these terms independently has the same meaning as R4, R5, R6, and R7.

[0057] Preferably, in embodiments of the benzofuran-2-one of formula (IV), R4, R5, R6, R7, R 4’ , R 5’ , R 6’ and R 7’ Each of these is independently hydrogen or a C1-C4 alkyl group, preferably hydrogen or a tertiary butyl group, and more preferably R4, R6, R 5’ and R 7’ It is a tertiary butyl, R5, R7, R 4’ and R 6’ is hydrogen; R 10 , R 11 , R 12 , R 13 and R 14 One of them is -OR 15 And R 10 , R 11 , R 12 , R 13 and R 14 The remainder is hydrogen or a C1-C4 alkyl group, preferably R 12 is -OR 15 And R 10 , or R 11 , R 13 and R 14 is hydrogen; R 15 is the basis of equation (VI-A), m is 0, Preferably, the bond of the group of formula (IV-A) to phenyl is at the para position.

[0058] In one preferred embodiment of the benzofuran-2-one of formula (IV), R4, R5, R6, and R7 are each independently of each other, being hydrogen or a C1-C8 alkyl group, preferably hydrogen or a C1-C4 alkyl group; R 10 , R 11 , R 12 , R13 and R 14 at least one of which is C1-C8 alkyl, and R 10 , R 11 , R 12 , R 13 and R 14 the remainder are hydrogen, preferably, R 10 , R 11 , R 12 , R 13 and R 14 two of which are C1-C4 alkyl, and R 10 , R 11 , R 12 , R 13 and R 14 the remainder are hydrogen.

[0059] In this embodiment of the benzofuran-2-one of formula (IV), R4 and R6 are C1-C4 alkyl, preferably tertiary butyl, and R5 and R7 are hydrogen, R 11 and R 12 are C1-C4 alkyl, preferably methyl, and R 10 , R 13 and R 14 are hydrogen, or R 10 and R 11 are C1-C4 alkyl, preferably methyl, and R 12 , R 13 and R 14 are preferably hydrogen.

[0060] Preferred examples of this embodiment are represented by benzofuran-2-ones of structural formula (IV-S4) and structural formula (IV-S5).

Chemical formula

[0061] Formula (IV-S4) corresponds to 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one, and formula (IV-S5) corresponds to 5,7-di-tert-butyl-3-(2,3-dimethylphenyl)-3H-benzofuran-2-one.

[0062] In a preferred embodiment, a mixture of compounds related to formulas (IV-S4) and (IV-S5) is used in the present invention. It is more preferable that the isomer corresponding to formula (IV-S4) is used as the main component of the mixture. Therefore, the ratio of the compound of formula (IV-S4) to the compound of formula (IV-S5) is preferably 51:49 to 99:1, preferably 60:40 to 99:1, more preferably 70:30 to 99:1, and more preferably 80:20 to 99:1 and 85:15 to 95:5.

[0063] In a particularly preferred embodiment of the benzofuran-2-one of formula (IV), R4, R5, R6, and R7 are each independently of each other, consisting of hydrogen or C1-C 12 Alkyl, preferably hydrogen or C1-C8 alkyl, preferably hydrogen or C1-C4 alkyl, Here, at least one of R4, R5, R6, and R7 is not hydrogen, R 10 , R 11 , R 12 , R 13 and R 14 Each of them is independent of the others, and is either hydrogen or C1-C 12 Alkyl, preferably hydrogen or C1-C8 alkyl, preferably hydrogen or C1-C4 alkyl, or -OR 15 And, Here, R 10 , R 11 , R 12 , R 13 and R 14 One of them is -OR 15 (R 15 is a base of formula (V) or formula (VI), and R 10 , R 11 , R 12 , R 13 and R14 At least one of them is C1~C 12 Alkyl, preferably C1-C8 alkyl, and more preferably C1-C4 alkyl, R 16 These are C1-C7 alkyl or substituted phenyl compounds. Y is oxygen, R 17 R 18 Together, they form a structure represented by formula (VI-C), R b1 , R b2 , R b3 , R b4 , R b5 and R b6 These are independently hydrogen or C1-C8 alkyl, preferably R b1 , R b2 , R b3 and R b4 It is a C1-C4 alkyl group, and R b5 and R b6 It is hydrogen, methyl, or ethyl.

[0064] In a particularly preferred embodiment of the benzofuran-2-one of formula (IV), R4, R5, R6, and R7 are each independently of each other, consisting of hydrogen or C1-C 12 Alkyl, preferably hydrogen or C1-C8 alkyl, preferably hydrogen or C1-C4 alkyl, Here, at least one of R4, R5, R6, and R7 is not hydrogen, R 10 , R 11 , R 12 , R 13 and R 14 Each of them is independent of the others, and is either hydrogen or C1-C 12 Alkyl, preferably hydrogen or C1-C8 alkyl, preferably hydrogen or C1-C4 alkyl, or -OR 15 And here, R 10 , R 11 , R 12 , R 13 and R 14 One of them is -OR 15 (R 15( is the basis of equation (V), and R 10 , R 11 , R 12 , R 13 and R 14 At least one of them is C1~C 12 Alkyl, preferably C1-C8 alkyl, and more preferably C1-C4 alkyl, R 16 is a C1-C7 alkyl group, preferably methyl, or R 16 This is a phenyl group having at least one C1-C4 alkyl group and at least one hydroxyl group.

[0065] In a further embodiment of the benzofuran-2-one of formula (IV), R4, R5, R6, and R7 are each independently of each other, consisting of hydrogen or C1-C 12 Alkyl, preferably hydrogen or C1-C8 alkyl, where at least one of R4, R5, R6 and R7 is not hydrogen. R 10 , R 11 , R 12 , R 13 and R 14 Each of them is independent of the others, and is either hydrogen or C1-C 12 Alkyl, preferably hydrogen or C1-C8 alkyl, or -OR 15 And here, R 10 , R 11 , R 12 , R 13 and R 14 One of them is -OR 15 (R15 is the basis of equation (V)), and R 10 , R 11 , R 12 , R 13 and R 14 At least one of them is C1~C 12 Alkyl, preferably C1-C8 alkyl, R 16 The C1-C7 alkyl group is preferably methyl.

[0066] Preferably, in this embodiment of benzofuran-2-one of formula (IV), R4 and R 11 Each of these is independently of the others, being hydrogen or a C1-C8 alkyl group, preferably hydrogen. R5, R7, R 12 and R 14 It is hydrogen, R6 and R 13 These are, C1~C, which are independent of each other. 12 It is alkyl, R 10 は-OR 15 And R 15 is the basis of equation (V), R 16 The C1-C7 alkyl group is preferably methyl.

[0067] A particularly preferred compound of this embodiment of benzofuranone of formula (IV) is formula (IV-S6). [ka]

[0068] Formula (IV-S6) corresponds to 2(3H)-benzofuranone,3-[2-(acetyloxy)-5-(1,1,3,3-tetramethylbutyl)phenyl]-5-(1,1,3,3-tetramethylbutyl)-.

[0069] In a particularly preferred further embodiment of the benzofuran-2-one of formula (IV), R4, R5, R6, and R7 are each independently of each other, being hydrogen or a C1-C8 alkyl group, preferably hydrogen or a C1-C4 alkyl group; R 10 , R 11 , R 12 , R 13 and R 14 Each of these is independently of the other, hydrogen or C1-C8 alkyl, preferably hydrogen or C1-C4 alkyl, or -OR 15 And here, R 10 , R 11 , R 12 , R 13 and R 14 One of them is -OR15 (R 15 (is the base of equation (VI), and R 10 , R 11 , R 12 , R 13 and R 14 At least one of them is a C1-C8 alkyl group, preferably a C1-C4 alkyl group. Y is oxygen, R 17 R 18 Together with, it forms a structure represented by equation (VI-C), R b1 , R b2 , R b3 , R b4 , R b5 and R b6 These are independently hydrogen or C1-C8 alkyl, preferably R b1 , R b2 , R b3 and R b4 It is a C1-C4 alkyl group, and R b5 and R b6 It is hydrogen, methyl, or ethyl.

[0070] In a more preferred form of this further embodiment of benzofuran-2-one of formula (IV), R4 and R6 are each independently a C1-C4 alkyl group, preferably both being tertiary butyl groups. R5 and R7 are hydrogen. R 10 and R 14 It is hydrogen, R 11 and R 13 Each of these is independently a C1-C4 alkyl group, preferably both being methyl. R 12 は-OR 15 And R 15 is the basis of equation (VI), Y is oxygen, R 17 R 18 Together, they form a structure represented by formula (VI-C), R b1 , Rb2 , R b3 and R b4 It is a tertiary butyl compound, R b5 is methyl or ethyl, preferably methyl; R b6 It is hydrogen.

[0071] A particularly desirable compound of this embodiment of benzofuranone of formula (IV) is represented by the structure of formula (IV-S7). [ka]

[0072] Formula (IV-S7) corresponds to 2(3H)-benzofuranone,5,7-bis(1,1-dimethylethyl)-3-[3,5-dimethyl-4-[[2,4,8,10-tetrakis(1,1-dimethylethyl)-12-methyl-12H-dibenzo[d,g][1,3,2]dioxaphosphosin-6-yl]oxy]phenyl].

[0073] In another preferred embodiment of the benzofuran-2-one of formula (IV), R4, R5, R6, and R7 are each independently of each other, being hydrogen or a C1-C8 alkyl group, preferably hydrogen or a C1-C4 alkyl group. R 10 , R 11 , R 12 , R 13 and R 14 Each of these is independently of the other, hydrogen or C1-C8 alkyl, preferably hydrogen or C1-C4 alkyl, or -OR 15 And here, R 10 , R 11 , R 12 , R 13 and R 14 One of them is -OR 15 (R 15 ( is the basis of equation (V), and R 10 , R 11 , R 12 , R 13 and R 14At least one of them is a C1-C8 alkyl group, preferably a C1-C4 alkyl group. R 16 This is a phenyl group having at least one C1-C4 alkyl group and at least one hydroxyl group.

[0074] In a more preferred embodiment of this embodiment of benzofuran-2-one of formula (IV), R6 is a C1-C4 alkyl group, more preferably a tertiary butyl group. R4, R5, and R7 are hydrogen. R 11 , R 12 and R 14 It is hydrogen, R 13 These are C1-C4 alkyl groups, more preferably tertiary butyl groups. R 10 は-OR 15 And R 15 is the basis of equation (V), R 16 This is a phenyl group having a C1-C4 alkyl group, more preferably a tertiary butyl group at positions 3 and 5, and a hydroxyl group at position 4.

[0075] A particularly desirable compound of this embodiment of benzofuran-2-one of formula (IV) is represented by the structure of formula (IV-S8). [ka]

[0076] Formula (IV-S8) corresponds to 3,5-di-tert-butyl-4-hydroxybenzoic acid [4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-1-benzofuran-3-yl)phenyl].

[0077] In another embodiment of the benzofuran-2-one of formula (IV), R4, R5, R6, and R7 are each independently of each other, being hydrogen or a C1-C8 alkyl group, preferably hydrogen or a C1-C4 alkyl group. R10 , R 11 , R 12 , R 13 and R 14 Each of them is independently of the others, hydrogen or a C1-C8 alkyl group, preferably hydrogen or a C1-C4 alkyl group, where R 10 , R 11 , R 12 , R 13 and R 14 One of them is -OR 15 (R 15 (is the base of equation (VA), A is C2~C 20 Containing an alkylene group or a divalent oligomeric oxyalkylene group, Z is C2~C 20 Containing alkyl or divalent oligomeric ester groups, G is a terminal group, consisting of hydrogen, C1-C 10 Selected from the group consisting of alkyl, alkylcarbonyl, and arylcarbonyl.

[0078] In a more specific form of this embodiment, R4 and R6 are C1-C4 alkyl, preferably tertiary butyl, and R5 and R7 are hydrogen. Furthermore, R 10 , R 11 , R 13 and R 14 It is all hydrogen, and R 12 は-OR 15 (R 15 ( is the base of formula (VA), where A, Z and G are defined above, more preferably A is a divalent oxyalkylene group comprising 1 to 50, preferably 1 to 20 oxyalkylene repeating units, where each oxyalkylene unit consists of 2 to 4 carbon atoms, more preferably optionally present, and Z is a divalent ester group comprising 0 to 50, preferably 0 to 20 ester repeating units, where each ester unit consists of 2 to 8, preferably 2 to 6 carbon atoms, and more preferably G is hydrogen or C1 to C 10 It is an alkyl group.

[0079] One such example of this benzofuran-2-one of formula (IV) is illustrated in formula (IV-S9). [ka] In the equation, s is an integer between 1 and 20, t is an integer between 0 and 20, and s + t is 3 or greater.

[0080] In a preferred embodiment, component (iii) of the stabilizer mixture is formula (VII): [ka] (In the formula, R 20 This is selected from hydrogen or an aliphatic group having 1 to 6 carbon atoms; R 21 A is an organic group having 1 to 30 carbon atoms; R 22 , R 23 , R 24 These are independently selected from hydrogen or C1-C4 alkyl groups; R 36 (This is a hydrogen or carbonyl group, preferably acetyl.) This is Chromanol.

[0081] In one embodiment, R in the compound of formula (VII) 20 The aliphatic group having 1 to 6 carbon atoms described in relation to may have 1, 2, 3, 4, 5, or 6 carbon atoms, for example, 1 to 4, 1 to 3, or 1 to 2 carbon atoms. In one embodiment, R 20 The aliphatic group having 1 to 6 carbon atoms described above can be selected from alkyl groups, where the alkyl group can be optionally interposed with one or more non-adjacent sulfur / oxygen atoms, and / or one or more non-adjacent carbon atoms in the alkyl group can be optionally replaced with -(CO)-O-.

[0082] In the compound of formula (VII), R 20This can be selected from hydrogen or C1-C6 alkyl, where the above C1-C6 alkyl can be optionally interposed by one or more non-adjacent sulfur / oxygen atoms, and / or one or more non-adjacent carbon atoms in the above alkyl can be optionally replaced by -(CO)-O-.

[0083] In the compound of formula (VII), R 20 This can be selected from hydrogen or C1-C4 alkyl (e.g., methyl, ethyl, propyl, or butyl), where the above C1-C4 alkyl can be optionally interposed by one or more non-adjacent sulfur / oxygen atoms, and / or one or more non-adjacent carbon atoms in the above alkyl can be optionally replaced by -(CO)-O-.

[0084] Suitable examples of C1-C6 alkyl groups, including C1-C4 alkyl groups, include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, and 2,2-dimethylbutyl. Examples include 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, ethenyl, 1-propenyl, 2-propenyl(allyl), 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and their isomers.

[0085] In one embodiment, the R of the compound of formula (VII) 21 The organic groups having 1 to 30 carbon atoms described in relation to the above can have 2 to 30 carbon atoms (e.g., 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, and 30), 6 to 30, 8 to 30, 8 to 22, and 10 to 22 carbon atoms. In one embodiment, R2 is hydrocarbyl. In one embodiment, R 21 It is linear or branched hydrocarbyl.

[0086] R 21 However, C1~C 30 Alkyl, or C2-C 30 In one embodiment, R2 is selected from alkenyls, more preferably C8~C 30 Alkyl or C8-C 30 Selected from alkenyls. In one embodiment, R 21 C8~C 22 Alkyl, or C8-C 22 Selected from alkenyls. In one embodiment, R 21 C 10 ~C 22 Alkyl, or C 10 ~C 22 Selected from alkenyls. In one embodiment, R 21 The alkenyls mentioned above may have 1 to 3 double bonds, for example, 1, 2, or 3 double bonds. 30 Alkyl and C8~C 30 The alkyl group can be optionally interposed by one or more non-adjacent sulfur / oxygen atoms, and / or one or more non-adjacent carbon atoms in the alkyl group can be optionally replaced by -(CO)-O-.

[0087] In the compound of formula (VII), R 22 , R 23 , R 24 R is independently selected from hydrogen or C1-C4 alkyl groups. In a preferred embodiment, R 22 , R 23 , R24 These are independently selected from hydrogen, methyl, or ethyl, preferably hydrogen or methyl.

[0088] In one embodiment, the variant of the compound of formula (VII) has the following meaning: R 20 This is selected from hydrogen or C1-C6 alkyl; R 21 C1~C 30 Alkyl, or C2-C 30 Selected from Alkenil; R 22 , R 23 , R 24 These are independently selected from hydrogen or C1-C4 alkyl groups; Here, the above alkyl (C1-C6 alkyl and C1-C 30 The alkyl group can be optionally interposed by one or more non-adjacent sulfur / oxygen atoms, and / or one or more non-adjacent carbon atoms in the alkyl group can be optionally replaced by -(CO)-O-.

[0089] In one embodiment, the variant of the compound of formula (VII) has the following meaning: R 20 This is selected from hydrogen or C1-C3 alkyl; R 21 C8~C 30 Alkyl, or C8-C 30 Selected from Alkenil; R 22 , R 23 , R 24 These are independently selected from hydrogen, methyl, or ethyl; Here, the above alkyl (C1-C3 alkyl and C8-C 30 The alkyl group can be optionally interposed by one or more non-adjacent sulfur / oxygen atoms, and / or one or more non-adjacent carbon atoms in the alkyl group can be optionally replaced by -(CO)-O-.

[0090] In one embodiment, the variant of the compound of formula (VII) has the following meaning: R 20 is selected from hydrogen or C1-C2 alkyl; R 21 C8~C 22 Alkyl, or C8-C 22 Selected from Alkenil; R 22 , R 23 , R 24 These are independently selected from hydrogen or methyl; Here, the above alkyl(C8~C 22 The alkyl group can be optionally interposed by one or more non-adjacent sulfur / oxygen atoms, and / or one or more non-adjacent carbon atoms in the alkyl group can be optionally replaced by -(CO)-O-.

[0091] In one embodiment, R 20 and R 24 At least one of (i.e., one or two) of R1 and R5 is not hydrogen. In one embodiment, at least one of (i.e., one or two) of R1 and R5 is methyl. In one embodiment, R 20 and R 24 Both are methyl.

[0092] In one embodiment, the compound of formula (VII) is of formula (VII-A): [ka] (In the formula, R 20 and R 24 These compounds independently comprise H or C1 alkyl (preferably methyl) compounds.

[0093] In one embodiment, R in formula (VII-A) 20 and R 24 It is a C1 alkyl group (i.e., methyl).

[0094] Compounds of formula (VII-A) have three chiral carbon atoms at the 2, 4', and 8' positions in their chemical structure. This includes all combinations of R and S stereoconfigurations at just one chiral carbon atom, including enantiomers and diastereomers, such as racemic mixtures. A compound of formula (VII-A) is, for example, α-tocopherol, i.e., R 20 is a C1 alkyl group, and R 24 A C1 alkyl group with stereochemistry 2R, 4'R, and 8'R is β-tocopherol, i.e., R 20 is a C1 alkyl group, and R 24 γ-tocopherol, which is hydrogen and has the stereochemistry 2R, 4'R, and 8'R, 20 is hydrogen, R 24 A C1 alkyl group with stereochemistry 2R, 4'R, and 8'R, or δ-tocopherol, i.e., R 20 is hydrogen, R 24 is hydrogen, with stereoconfigurations 2R, 4'R and 8'R. A mixture of compounds of formula (VII-A) is also suitable; for example, natural vitamin E or industrially synthesized vitamin E contains compounds of formula (VII-A). Preferably, R 20 and R 24 At least one of them is a C1 alkyl group. In particular, R 20 and R 24 It is a C1 alkyl group.

[0095] In one embodiment, the compound of formula (VII) (component (iii)) is selected from tocopherols, tocotrienols, and mixtures thereof. Examples of tocopherols include α-, β-, γ-, and δ-tocopherols. Examples of tocotrienols include α-, β-, γ-, and δ-tocotrienols.

[0096] In one embodiment, component (iii) comprises α-, β-, γ-, δ-tocopherol or α-, β-, γ-, δ-tocotrienol, or a mixture thereof.

[0097] In one embodiment, the compound of formula (VII) (component (iii)) is vitamin E. Vitamin E includes naturally occurring vitamin E and synthetically occurring vitamin E. In one embodiment, vitamin E is synthesized and is a mixture of stereoisomers.

[0098] In one embodiment, the compound of formula (VII) (component (iii)) is formula (VII-B): [ka] It is a compound of [the compound].

[0099] The compound associated with formula (VII-B) is 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-3,4-dihydrochromen-6-ol.

[0100] In one embodiment, the compound of formula (VII) (component (iii)) is formula (VII-C): [ka] It is a compound of [the compound].

[0101] The compound associated with formula (VII-C) is 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-3,4-dihydrochromen-6-yl acetate.

[0102] The compounds of formulas (VII-B) and (VII-C) each contain three chiral carbon atoms at the 2,4' and 8' positions in their respective chemical structures. All combinations of R and S stereoconfigurations at just one chiral carbon atom are included, including mixtures of enantiomers and diastereomers, such as racemic mixtures. In one embodiment, component (iii) is a racemic mixture of stereoisomers of formula (VII-B) and / or formula (VII-C).

[0103] The stabilizer mixture developed in this invention has been found to be effective in processing thermoplastic plastics such as polyolefins.

[0104] The components of the stabilizer mixture can be used in any suitable weight ratio sufficient to give the desired performance. A stabilizer mixture containing two of the three components (i) hydroxylamine or amine oxide; (ii) benzofuran-2-one according to formula (I); and (iii) chromanol, specifically (i) to (ii); or (i) to (iii), may in each case be in the range of 9:1 to 1:9, preferably 5:1 to 1:5, and more preferably 2:1 to 1:2. A stabilizer mixture containing the three components (i) hydroxylamine or amine oxide; (ii) benzofuran-2-one according to formula (I); and (iii) chromanol may have (i) to (ii) to (iii) in the range of 9:0.5:0.5 to 4.5:4.5:1, preferably 5:0.5:0.5 to 1:2.5:2.5, and more preferably 3:1:1 to 1:1:1.

[0105] In a particularly preferred embodiment, the stabilizer mixture comprises a combination of bis(hydrogenated palm oil alkyl)hydroxyamine and 2(3H)-benzofuranone,3-[2-(acetyloxy)-5-(1,1,3,3-tetramethylbutyl)phenyl]-5-(1,1,3,3-tetramethylbutyl)-(formula (IV-S6)). The weight ratio of the two components may be in the range of 9:1 to 1:9, preferably 5:1 to 1:5, and more preferably 2:1 to 1:2. The stabilizer mixture may further comprise other additives commonly used in stabilizer mixtures for processing thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0106] In a particularly preferred embodiment, the stabilizer mixture comprises a combination of N,N-di(hydrogenated fat)hydroxylamine and 2(3H)-benzofuranone,3-[2-(acetyloxy)-5-(1,1,3,3-tetramethylbutyl)phenyl]-5-(1,1,3,3-tetramethylbutyl)-(formula (IV-S6)). The weight ratio of the two components may be in the range of 9:1 to 1:9, preferably 5:1 to 1:5, and more preferably 2:1 to 1:2. The stabilizer mixture may further comprise other additives commonly used in stabilizer mixtures for processing thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0107] In a particularly preferred embodiment, the stabilizer mixture comprises a combination of bis(hydrogenated palm oil alkyl)hydroxyamine and 3,5-di-tert-butyl-4-hydroxybenzoic acid [4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-1-benzofuran-3-yl)phenyl] (formula IV-S8). The weight ratio of the two components may be in the range of 9:1 to 1:9, preferably 5:1 to 1:5, and more preferably 2:1 to 1:2. The stabilizer mixture may further comprise other additives commonly used in stabilizer mixtures for processing thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0108] In a particularly preferred embodiment, the stabilizer mixture comprises a combination of N,N-di(hydrogenated fat)hydroxylamine and 3,5-di-tert-butyl-4-hydroxybenzoic acid [4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-1-benzofuran-3-yl)phenyl] (formula IV-S8). The weight ratio of the two components may be in the range of 9:1 to 1:9, preferably 5:1 to 1:5, and more preferably 2:1 to 1:2. The stabilizer mixture may further comprise other additives commonly used in stabilizer mixtures for processing thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0109] In another particularly preferred embodiment, the stabilizer mixture comprises a combination of bis(hydrogenated palm oil alkyl)hydroxyamine and 2(3H)-benzofuranone,5,7-bis(1,1-dimethylethyl)-3-[3,5-dimethyl-4-[[2,4,8,10-tetrakis(1,1-dimethylethyl)-12-methyl-12H-dibenzo[d,g][1,3,2]dioxaphosphosin-6-yl]oxy]phenyl](formula (IV-S7)). The weight ratio of the two components may be in the range of 9:1 to 1:9, preferably 5:1 to 1:5, and more preferably 2:1 to 1:2. The stabilizer mixture may further comprise other additives commonly used in stabilizer mixtures used to process thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0110] In another particularly preferred embodiment, the stabilizer mixture comprises a combination of N,N-di(hydrogenated fat)hydroxylamine and 2(3H)-benzofuranone,5,7-bis(1,1-dimethylethyl)-3-[3,5-dimethyl-4-[[2,4,8,10-tetrakis(1,1-dimethylethyl)-12-methyl-12H-dibenzo[d,g][1,3,2]dioxaphosphosin-6-yl]oxy]phenyl](formula (IV-S7)). The weight ratio of the two components may be in the range of 9:1 to 1:9, preferably 5:1 to 1:5, and more preferably 2:1 to 1:2. The stabilizer mixture may further comprise other additives commonly used in stabilizer mixtures for processing thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0111] In a further particularly preferred embodiment, the stabilizer mixture comprises a combination of bis(hydrogenated palm oil alkyl)hydroxyamine and 2,5,7,8-tetramethyl2-(4,8,12-trimethyltridecyl)-3,4-dihydrochromen-6-ol(alpha-tocopherol) (formula VII-B). The weight ratio of the two components may be in the range of 9:1 to 1:9, preferably 5:1 to 1:5, and more preferably 2:1 to 1:2. The stabilizer mixture may further comprise other additives commonly used in stabilizer mixtures for processing thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0112] In a further particularly preferred embodiment, the stabilizer mixture comprises a combination of N,N-di(hydrogenated fat)hydroxylamine and 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-3,4-dihydrochromen-6-ol (alpha-tocopherol) (formula VII-B). The weight ratio of the two components may be in the range of 9:1 to 1:9, preferably 5:1 to 1:5, and more preferably 2:1 to 1:2. The stabilizer mixture may further comprise other additives commonly used in stabilizer mixtures for processing thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0113] In a further particularly preferred embodiment, the stabilizer mixture comprises a combination of 2(3H)-benzofuranone,3-[2-(acetyloxy)-5-(1,1,3,3-tetramethylbutyl)phenyl]-5-(1,1,3,3-tetramethylbutyl)-(formula (IV-S6)) and 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-3,4-dihydrochromen-6-ol(alpha-tocopherol)(formula VII-B). The weight ratio of the two components may be in the range of 9:1 to 1:9, preferably 5:1 to 1:5, and more preferably 2:1 to 1:2. The stabilizer mixture may further comprise other additives commonly used in stabilizer mixtures for processing thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0114] In a further particularly preferred embodiment, the stabilizer mixture comprises a combination of 3,5-di-tert-butyl-4-hydroxybenzoic acid [4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-1-benzofuran-3-yl)phenyl] (Formula IV-S8) and 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-3,4-dihydrochromen-6-ol (alpha-tocopherol) (Formula VII-B). The weight ratio of the two components may be in the range of 9:1 to 1:9, preferably 5:1 to 1:5, and more preferably 2:1 to 1:2. The stabilizer mixture may further comprise other additives commonly used in stabilizer mixtures for processing thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0115] In a further particularly preferred embodiment, the stabilizer mixture includes a combination of 2(3H)-benzofuranone,5,7-bis(1,1-dimethylethyl)-3-[3,5-dimethyl-4-[[2,4,8,10-tetrakis(1,1-dimethylethyl)-12-methyl-12H-dibenzo[d,g][1,3,2]dioxaphosphosin-6-yl]oxy]phenyl](formula (IV-S7)) and 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-3,4-dihydrochromen-6-ol(alpha-tocopherol)(formula VII-B). The weight ratio of the two components may be in the range of 9:1 to 1:9, preferably 5:1 to 1:5, and more preferably 2:1 to 1:2. The stabilizer mixture may further contain other additives commonly used in stabilizer mixtures used to process thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0116] In another particularly preferred embodiment, the stabilizer mixture comprises a combination of bis(hydrogenated palm oil alkyl)hydroxyamine, 2(3H)--benzofuranone,5,7-bis(1,1-dimethylethyl)-3-[3,5-dimethyl-4-[[2,4,8,10-tetrakis(1,1-dimethylethyl)-12-methyl-12H-dibenzo[d,g][1,3,2]dioxaphosphosin-6-yl]oxy]phenyl (formula (IV-S7)), and 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-3,4-dihydrochromen-6-ol (alpha-tocopherol) (formula VII-B). The weight ratio of the three components may be in the range of 9:0.5:0.5 to 4.5:4.5:1, preferably 5:0.5:0.5 to 1:2.5:2.5, and more preferably 3:1:1 to 1:1:1. The stabilizer mixture may further contain other additives commonly used in stabilizer mixtures used to process thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0117] In another particularly preferred embodiment, the stabilizer mixture comprises a combination of N,N-di(hydrogenated fat)hydroxylamine, 2(3H)-benzofuranone,5,7-bis(1,1-dimethylethyl)-3-[3,5-dimethyl-4-[[2,4,8,10-tetrakis(1,1-dimethylethyl)-12-methyl-12H-dibenzo[d,g][1,3,2]dioxaphosphosin-6-yl]oxy]phenyl](formula (IV-S7)), and 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-3,4-dihydrochromen-6-ol(alpha-tocopherol)(formula VII-B). The weight ratio of the three components may be in the range of 9:0.5:0.5 to 4.5:4.5:1, preferably 5:0.5:0.5 to 1:2.5:2.5, and more preferably 3:1:1 to 1:1:1. The stabilizer mixture may further contain other additives commonly used in stabilizer mixtures used to process thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0118] In another particularly preferred embodiment, the stabilizer mixture comprises a combination of bis(hydrogenated palm oil alkyl)hydroxyamine, 2(3H)-benzofuranone,3-[2-(acetyloxy)-5-(1,1,3,3-tetramethylbutyl)phenyl]-5-(1,1,3,3-tetramethylbutyl)-(formula (IV-S6)), and 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-3,4-dihydrochromen-6-ol (alpha-tocopherol)(formula VII-B). The weight ratio of the three components may be in the range of 9:0.5:0.5 to 4.5:4.5:1, preferably 5:0.5:0.5 to 1:2.5:2.5, and more preferably 3:1:1 to 1:1:1. The stabilizer mixture may further contain other additives commonly used in stabilizer mixtures for processing thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0119] In another particularly preferred embodiment, the stabilizer mixture comprises a combination of N,N-di(hydrogenated fat)hydroxylamine, 2(3H)-benzofuranone,3-[2-(acetyloxy)-5-(1,1,3,3-tetramethylbutyl)phenyl]-5-(1,1,3,3-tetramethylbutyl)-(formula (IV-S6)), and 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-3,4-dihydrochromen-6-ol (alpha-tocopherol)(formula VII-B). The weight ratio of the three components may be in the range of 9:0.5:0.5 to 4.5:4.5:1, preferably 5:0.5:0.5 to 1:2.5:2.5, and more preferably 3:1:1 to 1:1:1. The stabilizer mixture may further contain other additives commonly used in stabilizer mixtures for processing thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0120] In another particularly preferred embodiment, the stabilizer mixture comprises a combination of bis(hydrogenated palm oil alkyl)hydroxylamine, 3,5-di-tert-butyl-4-hydroxybenzoic acid [4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-1-benzofuran-3-yl)phenyl] (Formula IV-S8), and 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-3,4-dihydrochromen-6-ol (alpha-tocopherol) (Formula VII-B). The weight ratio of the three components may be in the range of 9:0.5:0.5 to 4.5:4.5:1, preferably 5:0.5:0.5 to 1:2.5:2.5, and more preferably 3:1:1 to 1:1:1. The stabilizer mixture may further contain other additives commonly used in stabilizer mixtures for processing thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0121] In another particularly preferred embodiment, the stabilizer mixture comprises a combination of N,N-di(hydrogenated fat)hydroxylamine, 3,5-di-tert-butyl-4-hydroxybenzoic acid [4-tert-butyl-2-(5-tert-butyl-2-oxo-3H-1-benzofuran-3-yl)phenyl] (Formula IV-S8), and 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-3,4-dihydrochromen-6-ol (alpha-tocopherol) (Formula VII-B). The weight ratio of the three components may be in the range of 9:0.5:0.5 to 4.5:4.5:1, preferably 5:0.5:0.5 to 1:2.5:2.5, and more preferably 3:1:1 to 1:1:1. The stabilizer mixture may further contain other additives commonly used in stabilizer mixtures for processing thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0122] In preferred embodiments, the stabilizer mixture comprises a combination of bis(hydrogenated palm oil alkyl)hydroxyamine and 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one (formula (IV-S4) and / or 5,7-di-tert-butyl-3-(2,3-dimethylphenyl)-3H-benzofuran-2-one (formula IV-S5)) (particularly as a 90:10 weight ratio of these two benzofuranones). The weight ratio of hydroxylamine to benzofuranone may be in the range of 9:1 to 1:9, preferably 5:1 to 1:5, and more preferably 2:1 to 1:2. The stabilizer mixture may further comprise other additives commonly used in stabilizer mixtures for processing thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0123] In preferred embodiments, the stabilizer mixture comprises a combination of N,N-di(hydrogenated fat)hydroxylamine and 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one (formula (IV-S4) and / or 5,7-di-tert-butyl-3-(2,3-dimethylphenyl)-3H-benzofuran-2-one (formula IV-S5)) (particularly as a 90:10 weight ratio of these two benzofurans). The weight ratio of hydroxylamine to benzofuranone may be in the range of 9:1 to 1:9, preferably 5:1 to 1:5, and more preferably 2:1 to 1:2. The stabilizer mixture may further comprise other additives commonly used in stabilizer mixtures for processing thermoplastic polymers, such as phosphites, e.g., tris(2,4-di-tert-butylphenyl)phosphite; light stabilizers; and acid scavengers.

[0124] Other preferred embodiments of the stabilizer mixture include the main stabilizer component: • 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-3,4-dihydrochromen-6-ol (alpha-tocopherol) (formula VII-B) and 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one (formula (IV-S4) and / or 5,7-di-tert-butyl-3-(2,3-dimethylphenyl)-3H-benzofuran-2-one (formula IV-S5) (especially as a 90:10 weight ratio of these two benzofurans). • Bis(hydrogenated palm oil alkyl)hydroxyamine and 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one (formula (IV-S4) and / or 5,7-di-tert-butyl-3-(2,3-dimethylphenyl)-3H-benzofuran-2-one (formula IV-S5) (especially as a 90:10 weight ratio of these two benzofurans) and 2,5,7,8-tetramethyl-2-(4,8,12-trimethyltridecyl)-3,4-dihydrochromen-6-ol (alpha-tocopherol) (formula VII-B) This includes combinations of the above.

[0125] Other preferred embodiments of the stabilizer mixture include the main stabilizer component: · Combined with 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one (formula (IV-S4) and / or 5,7-di-tert-butyl-3-(2,3-dimethylphenyl)-3H-benzofuran-2-one (formula IV-S5)) (especially as a 90:10 weight ratio of these two benzofuranones), dioctylmethylamine oxide, trioctylamine oxide, didecylmethylamine oxide, di(cocoalkyl)methylamine oxide, tri(cocoalkyl)amine oxide, di(fatalkyl)methylamine oxide, tri(fatalkyl)amine oxide, tri(C 14 ~C 24 ) Amine oxide, di(C 14 ~C 24A tertiary amine oxide, preferably an amine, bis(hydrogenated rapeseed alkyl)methyl, or N-oxide, selected from the group consisting of alkyl)methylamine oxide and a mixture containing any of the above. · Combined with 2(3H)-benzofuranone,3-[2-(acetyloxy)-5-(1,1,3,3-tetramethylbutyl)phenyl]-5-(1,1,3,3-tetramethylbutyl)-(formula (IV-S6)), dioctylmethylamine oxide, trioctylamine oxide, didecylmethylamine oxide, di(cocoalkyl)methylamine oxide, tri(cocoalkyl)amine oxide, di(fat alkyl)methylamine oxide, tri(fat alkyl)amine oxide, tri(C 14 ~C 24 ) Amine oxide, di(C 14 ~C 24 A tertiary amine oxide selected from the group consisting of alkyl)methylamine oxide and a mixture containing any of the above, preferably amine,bis(hydrogenated rapeseed alkyl)methyl,N-oxide. · Combined with 2(3H)-benzofuranone,5,7-bis(1,1-dimethylethyl)-3-[3,5-dimethyl-4-[[2,4,8,10-tetrakis(1,1-dimethylethyl)-12-methyl-12H-dibenzo[d,g][1,3,2]dioxaphosphosin-6-yl]oxy]phenyl] (formula (IV-S7)), dioctylmethylamine oxide, trioctylamine oxide, didecylmethylamine oxide, di(cocoalkyl)methylamine oxide, tri(cocoalkyl)amine oxide, di(fat alkyl)methylamine oxide, tri(fat alkyl)amine oxide, tri(C 14 ~C 24 ) Amine oxide, di(C 14 ~C 24 A tertiary amine oxide selected from the group consisting of alkyl)methylamine oxide and a mixture containing any of the above, preferably amine,bis(hydrogenated rapeseed alkyl)methyl,N-oxide. · Dioctylmethylamine oxide, trioctylamine oxide, didecylmethylamine oxide, di(cocoalkyl)methylamine oxide, tri(cocoalkyl)amine oxide, di(fat alkyl)methylamine oxide, tri(fat alkyl)amine oxide, tri(C) 14 ~C 24 ) Amine oxide, di(C 14 ~C 24 A tertiary amine oxide selected from the group consisting of alkyl)methylamine oxide and a mixture containing any of the above, preferably amine,bis(hydrogenated rapeseed alkyl)methyl,N-oxide. · Combined with 2,5,7,8-tetramethyl2-(4,8,12-trimethyltridecyl)-3,4-dihydrochromen-6-ol (alpha-tocopherol) (formula VII-B), dioctylmethylamine oxide, trioctylamine oxide, didecylmethylamine oxide, di(cocoalkyl)methylamine oxide, tri(cocoalkyl)amine oxide, di(fat alkyl)methylamine oxide, tri(fat alkyl)amine oxide, tri(C 14 ~C 24 ) Amine oxide, di(C 14 ~C 24 A tertiary amine oxide selected from the group consisting of alkyl)methylamine oxide and a mixture containing any of the above, preferably amine,bis(hydrogenated rapeseed alkyl)methyl,N-oxide This includes combinations of the above.

[0126] In one embodiment of the present invention, the stabilizer mixture comprises component (i), namely hydroxylamine (including any of the more specific embodiments described herein) or amine oxide (including any of the more specific embodiments described herein); and (ii) bensofran-2-one according to formula (I) (including any of the more specific embodiments described herein) and / or (iii) chromanol (including any of the more specific embodiments described herein). In a more preferred embodiment, the stabilizer mixture is used in an amount less than 500 ppm by total weight of components (i), (ii), and / or (iii) present in the stabilizer mixture, based on the weight of the thermoplastic polymer. More preferably, the amount used based on components (i), (ii), and / or (iii) should be less than 300 ppm, more preferably less than 250 ppm, preferably 200 ppm or less, more preferably 150 ppm or less, and even more preferably 100 ppm or less.

[0127] Accordingly, in this embodiment of the present invention, the stabilizer mixture comprises at least two components selected from (i), (ii), and (iii), and in any of the more specific embodiments described herein for each component and for the stabilizer mixture, components (i), (ii), and (iii) present in the stabilizer mixture are present in the thermoplastic polymer composition or used in a method or use for producing the thermoplastic polymer composition, based on the weight of the thermoplastic polymer, in amounts of less than 500 ppm, preferably less than 300 ppm, more preferably less than 250 ppm, preferably 200 ppm or less, more preferably 150 ppm or less, and even more preferably 100 ppm or less.

[0128] Generally, the stabilizer mixture may be present in the thermoplastic polymer composition in an amount of at least 40 ppm by the total weight of components (i), (ii), and / or (iii) present in the stabilizer mixture, based on the weight of the thermoplastic polymer, or it may be used in a method or use for producing the thermoplastic polymer composition. A suitable amount of the stabilizer mixture used may be in the range of 40 ppm to less than 500 ppm by the total weight of components (i), (ii), and (iii) present in the stabilizer mixture, based on the weight of the thermoplastic polymer, for example, 50 ppm to less than 300 ppm, 50 ppm to less than 250 ppm, 50 ppm to 200 ppm, 60 ppm to 150 ppm, or 60 ppm to 100 ppm.

[0129] In one particularly preferred embodiment of the present invention, the stabilizer mixture comprises (A)(i) hydroxylamine or amine oxide and (iii) chromanol; or (B)(ii) benzofuran-2-one of formula (I) and (iii) chromanol; or (C)(i) hydroxylamine or amine oxide and (ii) benzofuran-2-one of formula (I) and (iii) chromanol. Therefore, in this embodiment, (iii) chromanol must be present in the stabilizer mixture. This particularly preferred embodiment can be applied to various aspects (compositions, methods for preparing the compositions, and uses of the stabilizer mixture), where the composition comprises (a) a thermoplastic polymer, preferably a polyolefin, and (b) the stabilizer mixture. With respect to (A), components (i) and (iii) are present in the composition; (C) components (i), (ii), and (iii) are present in the composition in an amount of less than 500 ppm by the total weight of the components present in the stabilizer system based on the weight of the thermoplastic polymer; and (B) components (ii) and (iii) are present in the composition in an amount of less than 300 ppm, preferably less than 250 ppm, preferably 200 ppm or less, more preferably 150 ppm or less, and even more preferably 100 ppm or less by the weight of each component based on the weight of the thermoplastic polymer.

[0130] Components (i), (ii), and / or (iii) present in the stabilizer mixture of the present invention may be considered primary antioxidants. These primary antioxidants can capture and / or trap C-center radicals that are typically formed during the degradation of thermoplastic polymers.

[0131] In a preferred embodiment of the present invention, the stabilizer mixture may also contain a secondary antioxidant. More preferably, the secondary antioxidant is a phosphite or phosphonite, preferably a phosphite. Examples of suitable phosphites or phosphonites include trisalkyl(C) 12 ~C 15 Phosphite, triisodecyl phosphite, triisotridecyl phosphite, dioleyl hydrogen phosphite, triisooctyl phosphite, heptakis(dipropylene glycol) triphosphite, trilauryl trithiophosphite, tris(dipropylene glycol) phosphite, dimethyl hydrogen phosphite, dibutyl hydrogen phosphite, dilauryl hydrogen phosphite, tri-C 12 ~C 14 - It is a phosphite or bis(2-ethylhexyl) hydrogen phosphite. For example, it is a liquid such as di-n-octyl hydrogen phosphite or diisooctyl hydrogen phosphite, or for example triphenyl phosphite, tris(nonylphenyl) phosphite, phenyl diisodecyl phosphite, diphenyl isodecyl phosphite, [triphenyl phosphite, 1,4-cyclohexanedimethanol and polypropylene glycol ester, C 10 ~C 16 Other phosphites and phosphonates that are alkyl esters. Further optional phosphite or phosphonate additives include, for example, alkyl(C) 12 ~C 15 ) Bisphenol A phosphite, alkyl (C 10 )Bisphenol A phosphite, poly(dipropylene glycol)phenyl phosphite, tris(tridecyl) phosphite, diphenyl phosphite, dodecyl nonylphenol phosphite blend, phenylneopentylene glycol phosphite, poly4,4'-isopropylidenediphenol-C10 Alcohol phosphite, poly-4,4'-isopropylidenediphenol-C 12 ~ 15 Alcohol phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, C 12 ~C 18 Alkylbis[4-(1-methyl-1-phenyl-ethyl)phenyl]phosphite, C 12 ~C 18Alkenyl bis[4-(1-methyl-1-phenyl-ethyl)phenyl] phosphite, bis[4-(1-methyl-1-phenyl-ethyl)phenyl][(E)-octadeca-9-enyl l] phosphite, decyl bis[4-(1-methyl-1-phenyl-ethyl)phenyl] phosphite, didecyl[4-(1-methyl-1-phenyl-ethyl)phenyl] phosphite, [4-(1-methyl-1-phenyl-ethyl)phenyl] bis[(E)-octadeca-9-enyl 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(2,4-di-cumylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxy pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl) pentaerythritol Diphosphites, [2-tert-butyl-4-[1-[5-tert-butyl-4-di(tridecoxy)phosphanyloxy-2-methyl-phenyl]butyl]-5-methyl-phenyl]ditridecyl phosphite, tristearyl sorbitol triphosphite, for example, mixtures of at least two different tris(mono-C1~C8 alkyl)phenyl phosphites, such as those described in U.S. Patent No. 7468410 B2 as products of Examples 1 and 2, for example, mixtures 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25 and 26 as described in U.S. Patent No. 8008383 A mixture of phosphites containing at least two different tris(amylphenyl) phosphites, such as those described in Specification B2, tris[4-(1,1-dimethylpropyl)phenyl]phosphite, [2,4-bis(1,1-dimethylpropyl)phenyl]bis[4-(1,1-dimethylpropyl)phenyl]phosphite, bis[2,4-bis(1,A mixture of at least four different phosphites, including 1-dimethylpropyl)phenyl][4-(1,1-dimethylpropyl)phenyl]phosphite and tris[2,4-bis(1,1-dimethylpropyl)phenyl]phosphite, for example, a mixture of phosphites including at least two different tris(butylphenyl)phosphites, such as those described in U.S. Patent No. 8008383 B2 as mixtures 34, 35, 36, 37, 38, 39 and 40, for example, as the product of Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 and 17, as described in U.S. Patent No. 8304477. Oxyalkylene-bridged bis(di-C6aryl) diphosphites or oligomeric phosphites, such as those described in Specification B2, can be obtained by the condensation of (i) trichlorophosphan, (ii) a dihydroxyalkane intercalated with one or more oxygen atoms, and (iii) a mono-hydroxyC6arene under the removal of hydrogen chloride, for example, as products of Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 and 11, as specified in U.S. Patent No. 8563637. A polymer phosphite, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra-t, which can be obtained by transesterification under phenol removal of (i) a triphenyl phosphite, (ii) a dihydroxyalkane and / or bis(hydroxyalkyl)(alkyl)amine optionally interposed with one or more oxygen atoms, and (iii) a mono-hydroxyalkane optionally interposed with one or more oxygen atoms, as described in Specification B2, ert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphosine, bis(2,4-di-tert-butyl-6-methylphenyl)methylbis(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-dioxaphosphosine, 1,3,7,9-tetra-tert-butyl-11-octoxy-5H-benzo[d][1,3,2] The polymer consists of benzodioxaphosphosine, 2,2',2''-nitrilo[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite], phosphorous acid, triphenyl ester, α-hydro-ω-hydroxypoly[oxy(methyl-1,2-ethanediyl)], C10-16 alkyl ester, 2-ethylhexyl(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, phosphorous acid, and a mixture of 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triesters.

[0132] The following phosphites: Tris(2,4-di-tert-butylphenyl) phosphite (BASF), Tris(nonylphenyl) phosphite [ka] That is particularly preferable.

[0133] Phosphite or phosphonite may be used in amounts of 2% by weight or less of the thermoplastic polymer, for example, 0.01% to 2% by weight, or for example, 0.025% to 1% by weight.

[0134] The stabilizer mixture may also contain additional antioxidants. Typical additional antioxidants that may be included in the stabilizer mixture can be selected from the following list.

[0135] 1. Alkylated monophenols, e.g., 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol, 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-tricyclin Lohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols having linear or branched side chains, such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundecyl-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadecy-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridecyl-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyl-1'-tetradecylmethyl)phenol, and mixtures thereof.

[0136] 2. Alkylthiomethylphenols, for example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.

[0137] 3. Hydroquinones and alkylated hydroquinones, e.g., 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.

[0138] 4. Hydroxylated thiodiphenyl ethers, e.g., 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.

[0139] 5. Alkylidenebisphenols, e.g., 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'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4 ,6-di-tert-butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-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) Tan, 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, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene , bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-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.

[0140] 6. O-, N-, and S-benzyl compounds, e.g., 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

[0141] 7. Hydroxybenzylated malonates, e.g., dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecylmercaptoethyl-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.

[0142] 8. Aromatic hydroxybenzyl compounds, e.g., 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.

[0143] 9. Triazine compounds, e.g., 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-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5- Tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

[0144] 10. Benzyl phosphonates, 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, and calcium salts of monoethyl esters of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

[0145] 11. Acylaminophenols, e.g., 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

[0146] 12. A mixture of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid and a monohydric or polyhydric alcohol, such as methanol, ethanol, n-octanol, i-octanol, linear and branched C7-C9 alkanols, octadecanol, linear and branched C 13 ~C 15 Esters with alkanols, 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-thiaundadecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0147] 13. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols, e.g., 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)isopropyl alcohol Esters with anulates, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; and 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0148] 14. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, such as 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-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, and 4-hydroxymethyl-1-phosphine-2,6,7-trioxabicyclo[2.2.2]octane.

[0149] 15. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric or polyhydric alcohols, such as 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-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, and 4-hydroxymethyl-1-phosphine-2,6,7-trioxabicyclo[2.2.2]octane.

[0150] 16. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, e.g., 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-hydroxyphenyl]-propionyloxy)ethyl]oxamide (Naugard XL-1®, supplied by SI Group).

[0151] 17. Ascorbic acid (vitamin C).

[0152] 18. Amine antioxidants, e.g., N,N'-di-isopropyl-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-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine Amine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenyl Phenylenediamine, diphenylamine, N-aryldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, e.g., p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylamino Phenol, 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(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1',[3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, mixtures of mono- and dialkylated tert-butyl / tert-octyldiphenylamine, mixtures of mono- and dialkylated nonyldiphenylamine, mixtures of mono- and dialkylated dodecyldiphenylamine, mixtures of mono- and dialkylated isopropyl / isohexyldiphenylamine, mixtures of mono- and dialkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothi Adin, mixtures of mono- and dialkylated tert-butyl / tert-octylphenothiazine, mixtures of mono- and dialkylated tert-octylphenothiazine, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobuta-2-ene, N,N-bis(2,2,6,6-tetramethylpiperidi-4-l-hexamethylenediamine), bis(2,2,6,6-tetramethylpiperidi-4-l)sebacate, 2,2,6,6-tetramethylpiperidine-4-one, 2,2,6,6-tetramethylpiperidine-4-ol.

[0153] The stabilizer mixture of the present invention may also include a UV absorber and a light stabilizer. Typical examples of UV absorbers and light stabilizers are shown in the following list.

[0154] 1.2-(2'-hydroxyphenyl)benzotriazole, e.g., 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-( 3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxyphenyl) Xy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3' -tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)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-benzotriazole-2-ylphenol]; transesterification product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole and polyethylene glycol 300; [ka] (Here, R' = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazole-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.

[0155] 2.2-Hydroxybenzophenone, for example, 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

[0156] 3. Esters of substituted and unsubstituted benzoic acids, e.g., 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[0157] 4. Acrylates, for example, ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate, N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline, and tetra(α-cyano-β,β-diphenylacrylate)neopentyl.

[0158] 5. Nickel compounds, e.g., nickel complexes of 2,2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], e.g., 1:1 or 1:2 complexes with or without additional ligands such as n-butylamine, triethanolamine, or N-cyclohexyldiethanolamine; nickel dibutyldithiocarbamate; monoalkyl esters of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, e.g., nickel salts of methyl or ethyl esters; ketoximes, e.g., nickel complexes of 2-hydroxy-4-methylphenylundecylketoxime; nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.

[0159] 6. Steriohindated amine light stabilizers (HALS), e.g., 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(1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-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-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy C-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-tetramethylpiperidi-4-yl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidi-4-yl)succinate, bis-[2,2,6,6-tetramethyl-1-(undecyloxy)-piperidine-4-yl]ca - Bonate, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, condensates of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,Condensate of 6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropyl-amino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-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-2,2,6,6-tetramethyl A mixture of lupiperidines, a condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine; 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine and N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine; Methylpiperidine condensates; N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane, reaction products of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl -4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)-ethene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, diester of 4-methoxymethylenemalonic acid and 1,2,2,6,6-pentamethyl-4-hydroxy-piperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, maleic anhydride-α-olefin copolymer and 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,The reaction product with 6,6-pentamethyl-4-aminopiperidine is the oligomerization product of formal condensation of N,N'-bis(2,2,6,6-tetramethyl-1-propoxy-piperidine-4-yl)-hexane-1,6-diamine and 2,4-dichloro-6-{n-butyl-(2,2,6,6-tetramethyl-1-propoxy-piperidine-4-yl)-amino}-[1,3,5]triazine, which is end-capped with 2-chloro-4,6-bis(di-n-butylamino)-[1,3,5]triazine. A mixture of oligomeric compounds which are formal condensation products of N,N'-bis(2,2,6,6-tetramethylpiperidine-4-yl)-hexane-1,6-diamine and 2,4-dichloro-6-{n-butyl-(2,2,6,6-tetramethylpiperidine-4-yl)-amino}-[1,3,5]triazine end-capped with 2-chloro-4,6-bis(di-n-butylamino)-[1,3,5]triazine, 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-hexyl-1,6-diamine Tramethylpiperidine-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1,3,5-triazine, 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvor (Clariant), 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, 2,4-bis- Reaction product of [(1-cyclohexyloxy-2,2,6,6-piperidine-4-yl)butylamino]-6-chloro-s-triazine and N,N'-bis(3-amino-propyl)ethylenediamine), 1,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazine-3-on-4-yl)amino)-s-triazine, 1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperazine-3-on-4-yl)-amino)-s-triazine.

[0160] 7. Oxamides, such as 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides, and mixtures of o- and p-ethoxy-disubstituted oxanilides.

[0161] 8.2-(2-hydroxyphenyl)-1,3,5-triazine, e.g., 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-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-butyloxypropoxy)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-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-hexyl Oxy)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.

[0162] Other additives that may be included in the stabilizer mixture are as follows: Metal deactivators, such as N,N'-diphenyloxamide, N-salicyral-N'-salityroylhydrazine, N,N'-bis(salityroyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salityroylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoylbisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis-(salityroyl)oxalyl dihydrazide, and N,N'-bis(salityroyl)thiopropionyl dihydrazide.

[0163] Nitrones, such as N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-hexadecylnitrone, and nitrones derived from N,N-dialkylhydroxylamines derived from hydrogenated tallowamines.

[0164] Thiosinergists, such as dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate, and pentaerythritol tetrakis-[3-(n-lauryl)propionate].

[0165] Peroxide scavengers, such as α-thiodipropionic acid esters; for example, lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole; or zinc salts of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β-dodecylmercapto)propionate.

[0166] Polyamide stabilizers, such as copper salts combined with iodides and / or phosphorus compounds and divalent manganese salts.

[0167] Acid scavengers, such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate and zinc pyrocatecholate.

[0168] Fillers and reinforcing agents, such as calcium carbonate, silicates, glass fibers, glass beads, asbestos, talc, kaolin, bentonite, mica, hydrotalcite, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and other powders or fibers of natural products, and synthetic fibers.

[0169] Other additives include, for example, plasticizers, lubricants, rheological additives, catalysts, flow regulators, fluorescent whitening agents, flame retardants, antistatic agents, and foaming agents. Other additional additives that are useful to add include anti-agglutinating agents (glycerol monostearate, calcium stearate, etc.), anti-blocking agents, slip agents / processing aids (spinning oil, etc.), wetting aids, nucleating and clarifying agent additives, pigments, and matting agents (TiO2, etc.).

[0170] The thermoplastic polymer component in the present invention generally has thermoplastic properties that mean it can be molded into new shapes at high temperatures, for example, in the range of 135°C to 350°C, and especially 150°C to 340°C.

[0171] Thermoplastic polymers can be natural, semi-synthetic, or synthetic. Natural polymers are isolated from natural sources without further synthetic modification. Synthetic polymers do not contain polymer moieties isolated from natural sources. Semi-synthetic polymers contain at least one natural polymer moiety, which can be synthetically modified and / or reacted with monomers to form a semi-synthetic polymer.

[0172] The thermoplastic polymer may be a homopolymer that has been homopolymerized, i.e., polymerized in the absence of different monomers, or a copolymer based on at least two different monomers that have been copolymerized.

[0173] Examples of suitable thermoplastic polymers are: 1. Polymers of monoolefins and diolefins, e.g., polypropylene, polyisobutylene, polybuta-1-ene, poly-4-methylpenta-1-ene, polyvinylcyclohexane, polyisoprene, or polybutadiene, and polymers of cycloolefins, e.g., cyclopentene, or norbornene, polyethylene (which can be optionally crosslinked), e.g., high-density polyethylene (HDPE), high-density high-molecular-weight polyethylene (HDPE-HMW), high-density ultra-high-molecular-weight polyethylene (HDPE-UHMW), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), (VLDPE), and (ULDPE).

[0174] Polyolefins, i.e., polymers of monoolefins as exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be obtained by different methods, in particular by the following methods: a) Radical polymerization (usually under high pressure and high temperature). b) These can be prepared by catalytic polymerization using a catalyst that typically contains one or more metals from Group IVb, Vb, VIb (e.g., chromium) or Group VIII of the periodic table. These metals typically have one or more ligands, typically oxides, halides, alkoxides, esters, ethers, amines, alkyls, alkenyls, and / or aryls, which may be either π- or σ-coordinated. These metal complexes may be in free form or immobilized on a substrate, typically activated magnesium chloride, titanium(III) chloride, alumina, or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalysts may be used by themselves in polymerization, or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides, or metal alkyloxanes, wherein the metals are elements from Groups Ia, IIa, and / or IIIa of the periodic table. The activators can be easily modified with further ester, ether, amine, or silyl ether groups. These catalytic systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene, or single-site catalyst (SSC).

[0175] Mixtures of polymers as described in 2.1), such as mixtures of polypropylene and polyisobutylene, mixtures of polypropylene and polyethylene (e.g., PP / HDPE, PP / LDPE), and mixtures of different types of polyethylene (e.g., LDPE / HDPE).

[0176] 3. Copolymers of monoolefins and diolefins with each other or other vinyl monomers, e.g., ethylene / propylene copolymer, linear low-density polyethylene (LLDPE) and mixtures thereof with low-density polyethylene (LDPE), propylene / buta-1-ene copolymer, propylene / isobutylene copolymer, ethylene / buta-1-ene copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, ethylene / vinylcyclohexane copolymer, ethylene / cycloolefin copolymer (e.g., ethylene / norbornene such as COC), ethylene / 1-olefin copolymer (1-olefin is produced in situ), propylene / butadiene copolymer, isobutylene / isoprene copolymer, ethylene / Vinylcyclohexene copolymers, ethylene alkyl acrylate copolymers, ethylene alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers or ethylene / acrylic acid copolymers and their salts (ionomers), and terpolymers of ethylene with propylene and dienes, such as hexadiene, dicyclopentadiene or ethylidene norbornene, and mixtures of such copolymers mixed with each other and mixtures of the polymers of 1) above, such as polypropylene / ethylene-propylene copolymer, LDPE / ethylene-vinyl acetate copolymer (EVA), LDPE / ethylene-acrylic acid copolymer (EAA), LLDPE / EVA, LLDPE / EAA and polyalkylene / carbon monoxide alternating or random copolymers, and mixtures of these with other polymers, such as polyamides. Special copolymers of two monoolefins are pipe-grade polypropylene random copolymers that can be obtained by polymerization of more than 90% by weight of propylene and less than 10% by weight of ethylene, typically 2-6% by weight.

[0177] 4. Hydrocarbon resins (e.g., C5-C9) containing a hydrogenated modified product thereof (e.g., a tackifier), and mixtures of polyalkylene and starch.

[0178] The homopolymers and copolymers of 1.) to 4.) may have any stereostructure, such as syndiotactic, isotactic, hemiisotactic, or atactic; here, isotactic polymers are preferred. Stereoblock polymers are also included.

[0179] 5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

[0180] 6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers such as styrene, α-methylstyrene, vinyltoluene, all isomers, particularly p-vinyltoluene, ethylstyrene, propylstyrene, vinylbiphenyl, vinylnaphthalene, and vinylanthracene, and mixtures thereof. Homopolymers and copolymers may have any stereostructure, such as syndiotactic, isotactic, hemiisotactic, or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.

[0181] 6a. Copolymers comprising the aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, diene, nitrile, acid, maleic anhydride, maleimide, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene / butadiene, styrene / acrylonitrile, styrene / ethylene (copolymer), styrene alkyl methacrylate, styrene / butadiene alkyl acrylate, styrene / butadiene alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; mixtures of styrene copolymers with other polymers, for example polyacrylate, diene polymer or ethylene / propylene / diene polymer having high impact strength; and block copolymers of styrene such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

[0182] Hydrogenated aromatic polymers derived by the hydrogenation of polymers described in 6b.6, in particular, polycyclohexylethylene (PCHE), often called polycyclohexane (PVCH), which is prepared by the hydrogenation of atactic polystyrene.

[0183] Hydrogenated aromatic polymers derived from the hydrogenation of polymers described in 6c.6a.).

[0184] Homopolymers and copolymers may have any stereostructure, such as syndiotactic, isotactic, hemiisotactic, or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.

[0185] 7. Graft copolymers of vinyl aromatic monomers such as styrene or α-methylstyrene, e.g., polybutadiene with styrene, polybutadiene-styrene or polybutadiene-acrylonitrile copolymer with styrene; polybutadiene with styrene and acrylonitrile (or methacrylonitrile); polybutadiene with styrene, acrylonitrile and methyl methacrylate; polybutadiene with styrene and maleic anhydride; polybutadiene with styrene, acrylonitrile and maleic anhydride or maleimide; polybutadiene with styrene and maleimide; Copolymers grafted with styrene and alkyl acrylate or alkyl methacrylate onto polybutadiene; styrene and acrylonitrile onto ethylene / propylene / diene polymers; styrene and acrylonitrile onto polyalkyl acrylate or polyalkyl methacrylate; copolymers grafted with styrene and acrylonitrile onto acrylate / butadiene copolymers; and mixtures thereof with the copolymers listed in 6), for example, copolymers grafted with styrene and acrylonitrile onto copolymer mixtures known as ABS, MBS, ASA, or AES polymers.

[0186] 8. Halogen-containing polymers, for example, polychloroprene, chlorinated rubber, isobutylene-isoprene chlorinated and brominated copolymers (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homopolymers and copolymers, in particular polymers of halogen-containing vinyl compounds, for example, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, and their copolymers, for example, vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate, or vinyl chloride / vinyl acetate copolymers.

[0187] 9. Polymers derived from α,β-unsaturated acids, and their derivatives such as polyacrylates and polymethacrylates; polymethyl methacrylate, polyacrylamide, and polyacrylonitrile, which are impact-modified with butyl acrylate.

[0188] Copolymers obtained by copolymerizing the monomers described in 10.9) with each other or with other unsaturated monomers, such as acrylonitrile / butadiene copolymers, acrylonitrile alkyl acrylate copolymers, acrylonitrile alkoxyalkyl acrylates or acrylonitrile / halogenated vinyl copolymers or acrylonitrile alkyl methacrylate / butadiene copolymers.

[0189] 11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, vinyl polystearate, polyvinyl benzoate, vinyl polymaleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine, and copolymers thereof with the olefins described in 1) above.

[0190] 12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxides, and polypropylene oxides, or copolymers thereof with bisglycidyl ethers.

[0191] 13. Polyacetals such as polyoxymethylene and polyoxymethylene containing ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethane, acrylate or MBS.

[0192] 14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxide with styrene polymers or polyamides.

[0193] 15. Polyurethanes, for example, polyurethanes synthesized from polyols and aliphatic or aromatic polyisocyanates, for example, polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other hand, and precursors thereof.

[0194] Hydroxyl-terminated polyethers are known and can be prepared, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, or epichlorohydrin with themselves, for example, in the presence of BF3, or by the addition reaction of these epoxides, alone, in mixtures, or successively, with a starting component containing reactive hydrogen atoms, such as water, alcohol, ammonia, or amines, for example, ethylene glycol, propylene 1,3- and 1,2-glycol, trimethylolpropane, 4,4'-dihydroxydiphenylpropane, aniline, ethanolamine, or ethylenediamine. Sucrose polyethers are also suitable according to the present invention. In many cases, polyethers that mainly contain primary OH groups (up to 90% by weight, based on all OH groups present in the polyether) are preferred. Furthermore, polyethers modified with vinyl polymers, such as those formed by polymerizing styrene and acrylonitrile in the presence of a polyether, are as suitable as polybutadienes containing OH groups.

[0195] In particular, polyol compounds have a molecular weight of 400 to 10,000, especially 800 to 10,000, and contain several hydroxyl groups, especially 2 to 8 hydroxyl groups, and especially 2 to 4 hydroxyl groups.

[0196] Suitable polyisocyanates are aliphatic or aromatic, such as ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate, and any desired mixture of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanate Methylcyclohexane, 2,4- and 2,6-hexahydrotolylene diisocyanate, and any desired mixture of these isomers, hexahydro-1,3- and / or-1,4-phenylenediisocyanate, perhydro-2,4'- and / or-4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylenediisocyanate, 2,4- and 2,6-tolylene diisocyanate, and any desired mixture of these isomers. The desired mixtures include diphenylmethane-2,4'- and / or-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, triphenylmethane-4,4',4''-triisocyanate, polyphenyl-polymethylene polyisocyanates obtained by aniline-formaldehyde condensation followed by phosgenation, m- and p-isocyanatophenylsulfonyl isocyanates, perchlorinated aryl polyisocyanates, polyisocyanates containing carbodiimide groups, polyisocyanates containing allophanate groups, polyisocyanates containing isocyanurate groups, polyisocyanates containing urethane groups, polyisocyanates containing acylated urea groups, polyisocyanates containing biuret groups, polyisocyanates containing ester groups, reaction products of the above-mentioned isocyanates with acetals, and polyisocyanates containing high molecular weight fatty acid groups.

[0197] The isocyanate group-containing distillation residue obtained during the industrial preparation of isocyanates can be used as is, or dissolved in one or more of the polyisocyanates described above. Furthermore, any desired mixture of the polyisocyanates described above can be used.

[0198] Preferred are 2,4- or 2,6-tolylene diisocyanates and any desired mixture of these isomers ("TDI"), polyphenyl-polymethylene-polyisocyanates ("crude MDI") prepared by aniline-formaldehyde condensation followed by phosgenation, or polyisocyanates containing carbodiimide, urethane, allophanate, isocyanurate, urea, or biuret groups ("modified polyisocyanates").

[0199] Polyurethane can be homogeneous or cellular.

[0200] 16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or corresponding lactams, e.g., 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-xylylenediamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic acid or / and terephthalic acid, with or without elastomers as modifiers, e.g., poly-2,4,4-trimethylhex Shamethylene terephthalamide or poly-m-phenylene isophthalamide; and block copolymers of the aforementioned polyamide with polyolefins, olefin copolymers, ionomers, or chemically bonded or grafted elastomers; or block copolymers of the aforementioned polyamide with polyethers and, for example, polyethylene glycol, polypropylene glycol, or polytetramethylene glycol; and polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).

[0201] 17. Polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydantoins, and polybenzimidazoles.

[0202] 18. Polyesters derived from dicarboxylic acids and diols, and / or from hydroxycarboxylic acids or corresponding lactones or lactides, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate and polyhydroxybenzoate, and copolyether esters derived from hydroxyl-terminated polyethers, as well as polycarbonates and polyesters modified with MBS. Copolyesters may include, but are not limited to, polybutylene succinate / terephthalate, polybutylene adipate / terephthalate, polytetramethylene adipate / terephthalate, polybutylene succinate / adipate, polybutylene succinate / carbonate, poly-3-hydroxybutyrate / octanoate copolymer, and poly-3-hydroxybutyrate / hexanoate / decanoate copolymer. Furthermore, aliphatic polyesters may include, but are not limited to, the poly(hydroxyalkanoate) class, particularly poly(propiolactone), poly(butyrolactone), poly(pivalolactone), poly(valerolactone), and poly(caprolactone), polyethylene succinate, polypropylene succinate, polybutylene succinate, polyhexamethylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene oxalate, polypropylene oxalate, polybutylene oxalate, polyhexamethylene oxalate, polyethylene sebacate, polypropylene sebacate, polybutylene sebacate, and polylactic acid (PLA), as well as corresponding polyesters modified with polycarbonate or MBS.The term "polylactic acid (PLA)" preferably means homopolymers of poly-L-lactide and any blends or alloys with other polymers; copolymers of lactic acid or lactide with other monomers, such as hydroxycarboxylic acids, such as glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid and their cyclic products; the term "lactic acid" or "lactide" includes L-lactic acid, D-lactic acid, mixtures thereof and dimers, i.e., L-lactide, D-lactide, meso-lactide and any mixtures thereof.

[0203] 19. Polycarbonate and polyester carbonate.

[0204] 20. Polyketones.

[0205] 21. Polysulfones, polyethersulfones, and polyetherketones.

[0206] 22. Crosslinked polymers derived from aldehydes on the one hand and from phenol, urea, and melamine on the other hand, such as phenol / formaldehyde resins, urea / formaldehyde resins, and melamine / formaldehyde resins.

[0207] 23. Drying and non-drying alkyd resins.

[0208] 24. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols and vinyl compounds as crosslinking agents, and halogen-containing modified versions thereof that are low in flammability.

[0209] 25. Crosslinkable acrylic resins derived from substituted acrylates, such as epoxy acrylate, urethane acrylate, or polyester acrylate.

[0210] 26. Melamine resin, urea resin, isocyanate, isocyanurate, polyisocyanate, or alkyd resin, polyester resin, and acrylate resin crosslinked with epoxy resin.

[0211] 27. Crosslinked epoxy resins derived from aliphatic, alicyclic, heterocyclic, or aromatic glycidyl compounds, for example, products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with or without an accelerator using conventional curing agents such as acid anhydrides or amines.

[0212] 28. Natural polymers, such as cellulose, rubber, gelatin and chemically modified derivatives thereof, such as cellulose acetate, cellulose propionate and cellulose butyrate, or cellulose ethers such as methylcellulose; and rosin and derivatives thereof.

[0213] 29. Blends of the aforementioned polymers (polyblends), for example, PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

[0214] 30. Natural and synthetic organic substances that are pure monomer compounds or mixtures of such compounds, e.g., mineral oil, animal and vegetable fats, oils and waxes or oils, fats and waxes based on synthetic esters (e.g., phthalates, adipicates, phosphates or trimelliticates), and mixtures of synthetic esters and mineral oil in any weight ratio, typically used as spinning compositions, and aqueous emulsions of such materials.

[0215] 31. Aqueous emulsions of natural or synthetic rubber, e.g., natural latex or carboxylated styrene / butadiene copolymer latex.

[0216] At least a portion of thermoplastic polymers may include recycled thermoplastic polymers, often referred to as recycled materials.

[0217] Preferably, the thermoplastic polymer is polyethylene or polypropylene, such as polyolefins, more preferably any of the polyethylene or polypropylene polymers and copolymers listed in sections 1 to 3 and 29 of the above list of thermoplastic polymers.

[0218] A method for producing a thermoplastic polymer composition, wherein a stabilizer mixture is incorporated into the thermoplastic polymer before or during processing of the thermoplastic polymer.

[0219] The incorporation or application of the stabilizer mixture can be carried out in a processing apparatus, particularly in a heat-sensitive container equipped with a stirrer, which can preferably be closed. Examples of such heat-sensitive containers equipped with a stirrer include kneaders, extruders, mixers, or stirring tanks. Specific examples include single-screw extruders, reversing and co-rotating twin-screw extruders, planetary gear extruders, ring extruders, or co-kneaders. It is also possible to use a processing apparatus that includes at least one gas removal compartment, which can be set up in an atmosphere with low oxygen content or where oxygen is absent, for example, under a nitrogen atmosphere, and / or under a vacuum. The stabilizer mixture can be added directly to the processing apparatus.

[0220] The stabilizer mixture can be incorporated or applied at any stage of the processing of the thermoplastic polymer, particularly before or during the molding process of the thermoplastic polymer within the processing apparatus.

[0221] The stabilizer mixture can be incorporated or applied in the form of a dry powder, a melt, an encapsulated form such as encapsulation in wax or an auxiliary polymer, or a wet mixture such as a solution in an inert solvent, water or oil, a dispersion or suspension. In the case of a wet mixture of the stabilizer mixture, a dispersant or suspending agent may be present. A further form for incorporation is granules, obtained, for example, by compressing the powder of the stabilizer mixture.

[0222] The stabilizer mixture can also be incorporated or applied onto a thermoplastic polymer by spraying.

[0223] Further possibilities for incorporating or coating stabilizer mixtures into thermoplastic polymers include adding them before, during, or immediately after polymerization of the corresponding starting materials of the thermoplastic polymer, e.g., monomers. For example, spraying during the deactivation of the polymerization catalyst is particularly advantageous. If crosslinking occurs during the formation of the thermoplastic polymer, incorporating or coating before crosslinking is preferable.

[0224] The assembly or coating process is preferably a molding process, particularly injection molding, blow molding, compression molding, rotational molding, slush molding, or extrusion molding.

[0225] - A step of providing a thermoplastic polymer, - A step of incorporating a stabilizer mixture into a thermoplastic polymer, wherein the partial or complete incorporation is carried out at a temperature in the range of 135°C to 350°C, preferably 150°C to 340°C, particularly 180°C to 330°C, and very particularly 190°C to 320°C. A process including this is preferred.

[0226] A preferred process involves incorporating or applying a stabilizer mixture in the extruder during the processing of a thermoplastic polymer.

[0227] If one or more additional additives are used, the stabilizer mixture and the additional additives can be incorporated into or coated onto the thermoplastic polymer, individually or in combination with each other. If necessary, the individual components can be mixed with each other before being incorporated into the thermoplastic polymer, for example by dry blending, compression, melting, encapsulation with wax or auxiliary polymers, or as a wet mixture in the form of a solution, dispersion or suspension in an inert solvent, water or oil.

[0228] In a preferred embodiment, the stabilizer mixture is provided as a masterbatch. The stabilizer mixture and any one or more further additives can also be added to the thermoplastic polymer in the form of a masterbatch ("concentrate") containing the stabilizer mixture, one or more further additives, and the masterbatch polymer as an auxiliary polymer. The stabilizer mixture and any further additives can be incorporated into the masterbatch, for example, at a concentration of 1% to 40% by weight, preferably 2% to 20% by weight of the masterbatch. The masterbatch polymer content is the difference relative to 100% by weight of the masterbatch. The masterbatch polymer does not necessarily have to be the same polymer as the thermoplastic polymer.

[0229] Articles advantageously produced from compositions containing a mixture of thermoplastic polymer stabilizers can be molded articles. Examples of molded articles are as follows: I-1) Floating devices, marine applications, pontoons, buoys, plastic sheets for decks, piers, boats, kayaks, oars, and beach reinforcement.

[0230] I-2) Automotive applications, particularly bumpers, dashboards, batteries, rear and front linings, molded parts under the hood, rear shelves (hat shelves), trunk linings, interior linings, airbag covers, electronically molded parts for components (lights), dashboard panes, headlight lenses, instrument panels, exterior linings, upholstery materials, automotive lights, headlights, parking lights, taillights, stop lamps, interior and exterior trims, door panels, fuel tanks, front glazing, rear windows, seat backing materials, exterior panels, wire insulation, shaped extruded seals, cladding, pillar covers, chassis components, exhaust systems, fuel filters / fillers, fuel pumps, fuel tanks, side door belt moldings, convertible tops, side mirrors, exterior trims, fasteners / fixtures, front end modules, glass, hinges, locking systems, luggage / roof racks, pressed / stamped parts, seals, side impact protection, soundproofing / insulation materials, and sunroofs.

[0231] I-3) Road traffic devices, especially guideposts, road marking posts, car accessories, warning triangles, medical cases, helmets, and tires.

[0232] I-4) Devices for airplanes, trains, and automobiles (cars, motorcycles, trucks), including furnishings.

[0233] I-5) Devices for space applications, especially rockets and satellites, such as re-entry shields.

[0234] I-6) Devices for architecture and design, mining, acoustic equipment, street shelters and shelters.

[0235] II-1) Cases and covers for electrical appliances, general-purpose and electrical / electronic devices (personal computers, telephones, mobile phones, printers, televisions, audio and video devices), flower pots, satellite receivers, and panel devices.

[0236] II-2) Jackets made of steel and other materials such as fibers.

[0237] II-3) Electronic industrial devices, especially plugs, especially insulating materials for computer plugs, cases for electrical and electronic components, printed circuit boards, and materials for electronic data storage such as chips, check cards or credit cards.

[0238] II-4) Electrical appliances, especially washing machines, rotary dryers, ovens (microwave ovens), dishwashers, mixers, and irons.

[0239] II-5) Covers for lighting (e.g., streetlights, lampshades).

[0240] II-6) Applications in electric wires and cables (semiconductors, insulators, and cable jackets).

[0241] II-7) Foils for condensers, refrigerators, heating devices, air conditioners, sealing of electronic equipment, semiconductors, coffee makers, and vacuum cleaners.

[0242] III-1) Technical products such as gears, sliding fittings, spacers, screws, bolts, handles, and knobs.

[0243] III-2) Rotary blades, ventilation systems and wind turbine blades, solar cell systems, swimming pools, pool covers, pool liners, pond liners, closets, wardrobes, partition walls, slat walls, folding walls, roofs, shutters (e.g., roller shutters), fittings, connections between pipes, sleeves, and conveyor belts.

[0244] III-3) Sanitary items, especially shower rooms, toilet seats, covers, and sinks.

[0245] III-4) Hygiene products, especially diapers (for infants and adult incontinence), feminine hygiene products, shower curtains, brushes, mats, bathtubs, portable toilets, toothbrushes, and potty chairs.

[0246] III-5) Pipes (cross-linked or uncross-linked) for water, wastewater, and chemicals; pipes for protecting electric wires and cables; pipes for gas, oil, and sewage; gutters; downpipes; and drainage systems.

[0247] III-6) Any type of exterior shape material (window glass) and siding.

[0248] III-7) Glass substitutes, especially extruded or co-extruded glass, for buildings (monolithic, twin or multilayer), aircraft, schools, extruded sheets, window films for architectural glazing, trains, transport, sanitary products, and greenhouse glazing.

[0249] III-8) Plates (walls, cutting boards), extruded coatings (photographic paper, Tetra Pak and pipe coatings), silos, wood substitutes, plastic sheets, wood composites, walls, surfaces, furniture, decorative foils, flooring (interior and exterior), flooring, duckboard and tiles.

[0250] III-9) Intake and exhaust manifold.

[0251] III-10) Cement, concrete, composites and covers, siding and cladding, handrails, banisters, kitchen worktops, roofing, roofing sheets, tiles, and tarpaulins.

[0252] IV-1) Plates (walls and cutting boards), trays, artificial turf, synthetic covering materials (such as AstroTurf®), artificial covering materials for stadium rings (track and field), artificial flooring materials for athletic stadium rings, and tape.

[0253] IV-2) Continuous and short fiber fabrics, textiles (carpets / sanitary products / geotextiles / monofilaments / filters / wipes / curtains (shades) / medical), bulk fibers (for use in gowns / protective clothing, etc.), nets, ropes, cables, strings, cords, threads, safety seat belts, clothing, underwear, gloves; boots, rubber boots, innerwear, clothing, swimwear, sportswear, umbrellas (parasols, sunshades), parachutes, paragliders, sails, "balloon silk", camping equipment, tents, air beds, sunbeds, bulk bags, and bags. Nonwoven fabrics, such as medical fabrics and related clothing, industrial clothing, outdoor fabrics, household furniture and construction fabrics.

[0254] IV-3) Roofs, tunnels, dumps, pond membranes, insulation, covers, seals, dumps, wall roofing membranes, geomembranes, pools, curtains (sunshades), awnings, canopies, wallpaper, food packaging and packing (flexible and solid), medical packaging (flexible and solid), airbags / seat belts, armrests and headrests, carpets, center consoles, dashboards, cockpits, doors, overhead console modules, door trims, headliners, interior lighting, interior mirrors, parcel shelves, rear luggage covers, seats, steering columns, steering wheels, textiles and trunk trims.

[0255] V) Films (packaging, dumping, lamination, agriculture and horticulture, greenhouses, mulch, tunnels, silage), bale wraps, swimming pools, garbage bags, wallpaper, stretch films, raffia, desalination films, batteries, and connectors.

[0256] VI-1) Food packaging and wrapping (flexible and rigid), bottles.

[0257] VI-2) Storage systems for boxes (crates), luggage, chests, household boxes, pallets, shelves, trucks, screw boxes, packs, and cans.

[0258] VI-3) Cartridges, syringes, medical applications, transport containers, garbage baskets and trash cans, garbage bags, trash cans, dustbins, bin liners, wheeled trash cans, containers in general, tanks for water / used water / chemicals / gas / oil / gasoline / diesel; tank liners, boxes, wooden crates, battery cases, troughs, medical devices, e.g., pistons, ophthalmic applications, diagnostic devices, and pharmaceutical blister packaging.

[0259] VII-1) Extrusion coatings (photographic paper, Tetra Pak, pipe coatings), all kinds of household goods (e.g., electrical appliances, thermos bottles / clothes hangers), fastening systems, e.g., plugs, wire and cable clamps, zippers, closures, locks, and snap closures.

[0260] VII-2) Support devices, leisure items, e.g., sports and fitness devices, gymnastics mats, ski boots, inline skates, skis, Bigfoot, sports surfaces (e.g., tennis courts), screw tops, bottle and can tops and stoppers.

[0261] VII-3) All types of furniture, foam products (cushions, shock absorbers), foam, sponges, dish towels, mats, garden chairs, stadium seats, tables, sofas, toys, assembly kits (boards / figures / balls), playhouses, slides, and toy cars.

[0262] VII-4) Materials for optical and magnetic data storage.

[0263] VII-5) Kitchenware (eating, cooking, storage).

[0264] VII-6) Cases for CDs, cassettes and videotapes; DVD electronic items, all kinds of office supplies (ballpoint pens, stamps and ink pads, mice, shelves, trucks), bottles of all sizes and contents (beverages, detergents, perfumes and other cosmetics), and adhesive tapes.

[0265] VII-7) Footwear (shoes / soles), insoles, leggings, adhesives, structural adhesives, food boxes (fruits, vegetables, meat, fish), synthetic paper, bottle labels, benches, artificial joints (human), printing plates (flexographic), printed circuit boards, and display technology.

[0266] VII-8) Devices filled with polymers (talc, chalk, Chinese clay (kaolin), wollastonite, pigments, carbon black, TiO2, mica, nanocomposites, dolomite, silicate, glass, asbestos).

[0267] Preferred are articles that are shaped, such as films, pipes, profiles, bottles, tanks, containers, or fibers. More preferred are fabrics (continuous filaments, spunbond and meltblown fibers, such as bio-component fibers in any geometric shape (side-by-side, core-sheath, underwater island), along with nonwoven and woven articles ranging from fiber-based applications: medical clothing, geotextiles, diapers, filters, roofing, etc.), films (mainly BOPP films); injection-molded, blow-molded, and thermoformed extruded sheets, cables, etc. Particularly preferred are items that are either films or fibers.

[0268] Molded products are preferred. In particular, molding is carried out by injection molding, blow molding, compression molding, rotational molding, slush molding, or extrusion.

[0269] The following examples illustrate the present invention without limiting it. Unless otherwise stated, percentage values ​​are given by weight. [Examples]

[0270] Additives used in the examples Unless otherwise specified, all parts and percentages are given by weight. Unless otherwise specified, weight percentages (W%) are based on the whole composition excluding any volatile substances.

[0271] The primary and secondary antioxidant components are: Compound 1: Amine, bis(hydrogenated palm oil alkyl) hydroxy Compound 2: 2(3H)-benzofuranone,3-[2-(acetyloxy)-5-(1,1,3,3-tetramethylbutyl)phenyl]-5-(1,1,3,3-tetramethylbutyl)-[Formula IV-S6] Compound 3: 2(3H)-benzofuranone, 5,7-bis(1,1-dimethylethyl)-3-[3,5-dimethyl-4-[[2,4,8,10-tetrakis(1,1-dimethylethyl)-12-methyl-12H-dibenzo[d,g][1,3,2]dioxaphosphosin-6-yl]oxy]phenyl][Formula IV-S7] Compound 4: 2,5,7,8-Tetramethyl-2-(4,8,12-trimethyltridecyl)-3,4-dihydrochromen-6-ol (DL-alpha-tocopherol) [Formula VII-B] Compound 5: A mixture of 90% by weight of 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one corresponding to formula (IV-S4) and 10% by weight of 5,7-di-tert-butyl-3-(2,3-dimethylphenyl)-3H-benzofuran-2-one corresponding to formula (IV-S5). Compound 6: Tris(2,4-di-tert-butylphenyl) phosphite Compound 7: Pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionate That is the case.

[0272] Example 1 Compound manufacturing and multiple extrusion: Polypropylene HB 12XF (polymer 1) (nominal MFI 11, manufacturer Polychim(F)) was used with a base additive package containing 0.084% tris(2,4-di-tert-butylphenyl) phosphite + 0.028% poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol-,1,4-butanediic acid) + 0.15% 1,6-hexanediamine (reaction product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidine-yl), 2,4,6-trichloro-1,3,5-triazine) + 0.03% magnesium / aluminum hydrotalcite.

[0273] The formulation was prepared by powder blending in a Mixaco Lab CM 12 high-speed mixer. The compound was manufactured at 230°C under a nitrogen atmosphere using a Collin 25×42D twin-screw extruder. The compound was further extruded three times at 280°C in a Goettfert ES 30L / D25 single-screw extruder.

[0274] The melt flow index (MFI) was measured at 230°C using 2.16 kg at Goettfert MI Robo (Goettfert Werkstoff Pruefmaschinen GmbH (D)) according to EN ISO 1133. An increase in the melt flow index indicates a decrease in the melt viscosity of the polymer, and in the case of polymer 1, it correlates with chain breakdown and a decrease in the molecular weight of polymer 1. Therefore, MFI measurement is useful in indicating the efficiency of additives for stabilizing the polymer.

[0275] [Table 1]

[0276] The results show that the Invention Tests 1-5, using an inventive stabilizer mixture containing at least two of components (i), (ii), and (iii) as primary antioxidants, provide remarkably better overall MFI control compared to comparative examples using the corresponding compounds alone. Invention Tests 2, 3, 4, and 5 all show improved MFI results compared to the corresponding MFI results for each single component used alone. Invention Test 1 shows a significantly improved MFI result compared to the use of compound 1 alone and an MFI result comparable to compound 2 used alone.

[0277] Example 2 Manufacturing of extruded fiber yarn materials: Polymer 1 was used with a base additive package containing 0.084% tris(2,4-di-tert-butylphenyl) phosphite + 0.028% poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol-,1,4-butanediic acid) + 0.15% 1,6-hexanediamine (reaction product of N,N'-bis(2,2,6,6-tetramethyl-4-piperidine-yl) and 2,4,6-trichloro-1,3,5-triazine) + 0.03% magnesium / aluminum hydrotalcite.

[0278] The formulation was prepared by powder blending in an MTI / M35 high-speed mixer.

[0279] The compound was manufactured at 230°C under a nitrogen atmosphere using a Collin 25×42D twin-screw extruder. The compound was used to spin fibers at 240°C on a Busschaert Spinboy II. Fiber yarn material for MFI testing was taken before drawing and without applying the spinning finish.

[0280] The melt flow index (MFI) was measured at 230°C using 2.16 kg at Goettfert MI Robo (Goettfert Werkstoff Pruefmaschinen GmbH (D)) according to EN ISO 1133. An increase in the melt flow index indicates a decrease in the melt viscosity of the polymer, and in the case of polymer 1, it correlates with chain breakdown and a decrease in the molecular weight of polymer 1. Therefore, MFI measurement is useful in indicating the efficiency of additives for stabilizing the polymer.

[0281] [Table 2]

[0282] The results showed that the stabilizer mixture of the present invention, comprising at least two of the primary antioxidants (i), (ii), and (iii), in tests 6-8 of the present invention provided an unexpectedly increased MFI control compared to Comparative Example 5, which used a single compound 1.

[0283] Example 3 Compound manufacturing and multiple-pass extrusion: Polypropylene A10TB (polymer 2) (nominal MFI 3, manufacturer Polychim(F)) was used with a base additive package containing 0.04% tris(2,4-di-tert-butylphenyl) phosphite + 0.03% poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol-,1,4-butanediic acid) + 0.05% calcium stearate.

[0284] The formulation was prepared by powder blending in a high-speed mixer. Compound production was carried out in the first step at 250°C under a nitrogen atmosphere using a single-screw extruder. The compound was re-extruded four times at 250°C in steps 2-5.

[0285] The melt flow index (MFI) was measured at 230°C using 2.16 kg at Goettfert MI Robo (Goettfert Werkstoff Pruefmaschinen GmbH(D)) according to EN ISO 1133.

[0286] An increase in the melt flow index indicates a decrease in the melt viscosity of the polymer. In the case of polymer 2, this correlates with chain breakdown and a decrease in the molecular weight of polymer 2. MFI measurement helps to indicate the efficiency of additives for stabilizing the polymer.

[0287] [Table 3]

[0288] The results show that Test 9 of the present invention, using a stabilizer mixture containing at least two of components (i), (ii), and (iii) used according to the present invention as primary antioxidants, provides remarkably improved MFI control when compared to comparative tests 7 and 8 using only a single compound, and to comparative test 6 using only a secondary antioxidant.

[0289] Example 4 Compound manufacturing and multiple-pass extrusion: Polymer 1 was used with a base additive package containing 0.084% tris(2,4-di-tert-butylphenyl) phosphite + 0.028% poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol-,1,4-butanediic acid) + 0.15% 1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl4-piperidine-yl), 2,4,6-trichloro-1,3,5-triazine reaction product + 0.03% magnesium / aluminum hydrotalcite.

[0290] The formulation was prepared by powder blending in a Mixaco Lab CM 12 high-speed mixer. The compound was manufactured at 230°C under a nitrogen atmosphere using a Collin 25×42D twin-screw extruder. The compound was further extruded three times at 280°C in a Goettfert ES 30L / D25 single-screw extruder. 2 mm plaques were compression molded at 230°C with a compression molding time of 3 minutes.

[0291] Color measurement: Color measurements were performed after compression molding and after 24 hours of exposure to NOx gas using parameters set according to AATCC 164.

[0292] Color was measured using a Datacolor 800 from Datacolor AG Europe, Switzerland, in accordance with DIN 6167. The yellowness index (YI) (unitless) was measured relative to the initial color of the plaque and is taken as the square root of the square of the difference in L*, a*, and b* CIELAB color coordinates at recall minus zero, as defined in ISO 11664-4. Delta E, measured in CIELAB units, provided information on the change in color during 24 hours of gas exposure relative to the initial value.

[0293] [Table 4]

[0294] The results demonstrate that tests 10, 11, and 12 of the present invention, using stabilizer mixtures containing at least two of components (i), (ii), and (iii) used according to the present invention as primary antioxidants, yield better YI values ​​than those that would be expected from the combination of each component.

[0295] The results also show that Test 10, using the combination of compound 1 and compound 2, and Test 12, using the combination of compound 1 and compound 4, gave significantly better Delta E values ​​after 24 hours of gas fading compared to what would be expected from each of these component combinations.

[0296] Inventive test 11, using a combination of compound 1 and compound 3, yielded a Delta E value after 24 hours of gas fading, compared to the corresponding use of compound 1 and compound 3 when used individually. The test work contained herein also demonstrates that the combination of compound 1 and compound 3 as a stabilizer mixture at the same doses as in this test results in unexpectedly improved YI values ​​and significantly improved MFI control values. Thus, the combination of compounds 1 and 3 is shown to provide improved overall performance.

[0297] Example 5 Compound manufacturing and multiple-pass extrusion: Polypropylene HA 10XT (polymer 3) (nominal MFI 3, manufacturer Polychim(F)) was used with a base additive package containing 0.06% tris(2,4-di-tert-butylphenyl) phosphite + 0.03% calcium stearate.

[0298] The formulation was prepared by powder blending in a Mixaco Lab CM 12 high-speed mixer. The compound was manufactured at 230°C under a nitrogen atmosphere using a Bersterff ZE25Ax47D twin-screw extruder. The compound was then extruded three times at 280°C in a Collin E30 P 25D single-screw extruder.

[0299] The melt flow index (MFI) was measured at 230°C using 2.16 kg at Goettfert MI Robo (Goettfert Werkstoff Pruefmaschinen GmbH (D)) according to EN ISO 1133. An increase in the melt flow index indicates a decrease in the melt viscosity of the polymer, and in the case of polymer 3, it correlates with chain breakdown and a decrease in the molecular weight of polymer 3. Therefore, MFI measurement is useful in indicating the efficiency of additives for stabilizing the polymer.

[0300] [Table 5]

[0301] The results show that the present invention tests 13-15, using an inventive stabilizer mixture containing at least two of components (i), (ii), and (iii) as primary antioxidants, provide remarkably improved behavior in the MFI control compared to comparative examples using the corresponding compounds alone. Inventive tests 13 and 15 show improved MFI results compared to the corresponding MFI results for each single component used alone. Inventive test 14 shows a significantly improved MFI result compared to the use of compound 1 alone and an MFI result comparable to compound 4 used alone.

[0302] Example 6 Compound manufacturing and multiple extrusion: Polyethylene MG 9641 (polymer 4) (nominal MFI 8, manufacturer Borealis) was used with a base additive package containing 0.05% tris(2,4-di-tert-butylphenyl) phosphite + 0.03% calcium stearate.

[0303] The formulation was prepared by powder blending in a Mixaco Lab CM 12 high-speed mixer. The compound was manufactured at 220°C under a nitrogen atmosphere using a Bersterff ZE25Ax47D twin-screw extruder. The compound was then extruded three times at 260°C in a Collin E30 P 25D single-screw extruder.

[0304] The melt flow index (MFI) was measured at 190°C using 2.16 kg at Goettfert MI Robo (Goettfert Werkstoff Pruefmaschinen GmbH (D)) according to EN ISO 1133. A decrease in the melt flow index indicates an increase in the melt viscosity of the polymer, and in the case of polymer 4, it correlates with typical crosslinking and an increase in the molecular weight of polymer 4. Therefore, MFI measurement is useful in indicating the efficiency of additives for stabilizing the polymer. In this case, it is important to prevent or reduce crosslinking of polyethylene polymer 4, and thus, improvement in avoiding crosslinking will be indicated by an increase in the MFI value.

[0305] [Table 6]

[0306] The results show that Test 16 of the present invention, using a stabilizer mixture containing components (i) and (iii) as primary antioxidants, provides remarkably improved behavior in the MFI control compared to a comparative example using the corresponding compound alone.

Claims

1. a) Thermoplastic polymer, preferably polyolefin; b) A stabilizer mixture comprising at least two components selected from (i), (ii), and (iii) A composition comprising, During the ceremony, Component (i) is a hydroxylamine or amine oxide; Component (ii) is benzofuran-2-one of formula (I); The component (iii) is chromanol, 【Chemistry 1】 During the ceremony, R ３ This is a substituted carbocyclic or heterocyclic aromatic ring system. R ４ , R ５ , R ６ and R ７ Each substituent is independently selected from hydrogen or chloro; hydroxy; a substituted or unsubstituted hydrocarbyl group optionally containing at least one heteroatom; a substituted or unsubstituted hydrocarbyloxy group optionally containing at least one further heteroatom; a substituted or unsubstituted cyclohydrocarbyl group optionally containing at least one heteroatom; or a substituent optionally containing at least one further heteroatom. If the stabilizer mixture contains components (i), (ii), and / or (iii), then it is present in the composition in an amount of less than 500 ppm by total weight of components (i), (ii), and / or (iii) present in the stabilizer mixture, based on the weight of the thermoplastic polymer. If the stabilizer mixture contains components (ii) and (iii) without (i), it is present in the composition in an amount of less than 300 ppm, preferably less than 250 ppm, preferably 200 ppm or less, more preferably 150 ppm or less, and even more preferably 100 ppm or less, based on the weight of the thermoplastic polymer.

2. Component (i) is given by formula (II): 【Chemistry 2】 (wherein, R １ and R ２ are each independently a C ８ -C ３０ alkyl group, preferably a C １２ -C ３０ alkyl group, more preferably a C １６ -C ２０ alkyl group selected from) The composition according to claim 1, wherein the hydroxylamine has the following properties.

3. Component (i) is amine oxide formula (III): 【Transformation 3】 (In the formula, R ８ and R ９ Each of them is independent of C ８ ~C ３０ Alkyl alkyl group, preferably C １２ ~C ３０ Alkyl alkyl group, comfortable C １４ ~C ２４ (Selected from alkyl groups) The composition according to claim 1.

4. Component (ii) is formula (IV): 【Chemistry 4】 [In the formula, R ４ , R ５ , R ６ and R ７ Each substituent is independently selected from hydrogen or chloro; hydroxy; a substituted or unsubstituted hydrocarbyl group optionally containing at least one heteroatom; a substituted or unsubstituted hydrocarbyloxy group optionally containing at least one further heteroatom; a substituted or unsubstituted cyclohydrocarbyl group optionally containing at least one heteroatom; or a substituent optionally containing at least one further heteroatom, preferably R ４ , R ５ , R ６ and R ７ Each of them is independently of the other, either hydrogen or C １ ~C ８ It is alkyl; R １０ , R １１ , R １２ , R １３ and R １４ These are, independently of each other, hydrogen, hydroxyl, and C. １ ~C １２ Alkyl, -OR １５ , -NR ３４ R ３５ or substituents having one or repeating alkylene oxide units, where R １０ , R １１ , R １２ , R １３ and R １４ At least one of them is not hydrogen, R １０ , R １１ , R １２ , R １３ and R １４ Only one of them is -OR １５ or -NR ３４ R ３５ And, Here, R １５ is a base of formula (V), or a base of formula (V-A), or a base of formula (VI), R ３４ is the basis of equation (VI-A), R ３５ is hydrogen or C １ ~C ８ It is alkyl; 【Transformation 5】 A is C ２ ~C ２０ Containing an alkylene group or a divalent oligomeric oxyalkylene group, Z is C ２ ~C ２０ Containing alkyl or divalent oligomeric ester groups, G is a terminal group, and consists of hydrogen and C. １ ~C １０ Selected from the group consisting of alkyl, alkylcarbonyl, and arylcarbonyl, R １６ is a substitution or non-substitution C １ ~C １２ Alkyl alkyl groups; substituted or unsubstituted C ４ ~C ８ A cycloalkyl-substituted or unsubstituted C5-C6 aryl group, preferably a substituted or unsubstituted phenyl group, preferably R １６ C １ ~C １２ It is an alkyl or substituted phenyl group; Y is oxygen or a covalent bond; If Y is oxygen, R １７ and R １８ These are, independently, equation (VI-A): 【Transformation 6】 (Each R １９ The bases or bases(s) are independent of each other, C １ ~C ８ It is alkyl; m is an integer between 0 and 4; R ４’ , R ５’ , R ６’ and R ７’ Each of them is independent of R ４ , R ５ , R ６ and R ７ (Having the same meaning) It is the basis of; or R １７ and R １８ are each independently of the other unsubstituted or substituted by C １ to C ８ alkyl, C １０ to C ８ alkoxy, halogen or phenyl, C ６ to C １０ aryl; C １ to C １８ alkyl; C ３ to C １６ cycloalkyl; C ７ to C １３ aralkyl; C ２ to C １８ alkenyl; interrupted by one or more oxygen atoms, C ２ to C ３０ alkyl; or interrupted by one sulfur atom, C ２ to C １６ alkyl; or R １７ R １８ Along with, equation (VI-B), (VI-C), or (VI-D): 【Transformation 7】 (R ａ１ , R ａ２ , R ａ３ and R ａ４ These are, independently of each other, hydrogen or C １ ~C ８ It is alkyl, R ｂ１ , R ｂ２ , R ｂ３ , R ｂ４ , R ｂ５ and R ｂ６ These are, independently of each other, hydrogen or C １ ~C ８ It is alkyl, R ｃ１ , R ｃ２ , R ｃ３ and R ｃ４ These are, independently of each other, hydrogen or C １ ~C ８ (It is alkyl.) It forms one of the structures, If Y is a covalent bond, R １７ is equation (VI-A), or R １７ is either non-substituted or C １ ~C ８ Alkyl, C １ ~C ８ Substituted by an alkoxy, halogen, or one phenyl, C ６ ~C １０ Ariel; C １ ~C １８ Alkyl; C ３ ~C １６ Cycloalkyl; C ７ ~C １３ Aralquil; C ２ ~C １８ Alkenyl; C, which is interspersed with one or more oxygen atoms. ２ ~C ３０ Alkyl; or C, which is interspersed with one sulfur atom. ２ ~C １６ It is alkyl, R １８ is either non-substituted or C １ ~C ８ Alkyl, C １ ~C ８ Substituted by an alkoxy, halogen, or one phenyl, C ６ ~C １０ [It is an aryl or halogen.] The composition according to any one of claims 1 to 3, wherein the benzofuran-2-one is benzofuran-2-one.

5. Component (iii) is formula (VII): 【Transformation 8】 (In the formula, R ２０ This is selected from hydrogen or an aliphatic group having 1 to 6 carbon atoms; R ２１ This is an organic group having 1 to 30 carbon atoms; R ２２ , R ２３ , R ２４ These are, independently of each other, hydrogen or C １ ~C ４ (Selected from alkyl groups) The composition according to any one of claims 1 to 4, wherein the composition is chromanol.

6. The composition according to any one of claims 1 to 5, wherein if the stabilizer mixture contains only two of the three components (i), (ii), and (iii), the weight ratio of (i) to (ii); (i) to (iii); or (ii) to (iii) in the stabilizer mixture is 9:1 to 1:9, preferably 5:1 to 1:5, more preferably 2:1 to 1:2; and if the stabilizer mixture contains all three of the components (i), (ii), and (iii), the weight ratio of (i) to (ii) to (iii) in the stabilizer mixture is 9:0.5:0.5 to 4.5:4.5:1, preferably 5:0.5:0.5 to 1:2.5:2.5, more preferably 3:1:1 to 1:1:

1.

7. The composition according to any one of claims 1 to 6, wherein the stabilizer mixture comprises components (i), (ii), and / or (iii), and the total weight of components (i), (ii), and / or (iii) present in the stabilizer mixture, based on the weight of the thermoplastic polymer, is less than 300 ppm, preferably less than 250 ppm, preferably 200 ppm or less, more preferably 150 ppm or less, and even more preferably 100 ppm or less.

8. The composition according to any one of claims 1 to 7, wherein the stabilizer mixture further comprises a secondary antioxidant containing a phosphite.

9. The composition according to any one of claims 1 to 8, wherein the stabilizer mixture further comprises at least one additive selected from the group consisting of a light stabilizer such as a hindered amine light stabilizer (HALS) and an acid scavenger.

10. A composition according to any one of claims 1 to 9, which is processed into a molded product.

11. The composition according to any one of claims 1 to 10, wherein the polyolefin is polypropylene or polyethylene.

12. A method for preparing a composition according to any one of claims 1 to 11, comprising the step of processing the thermoplastic polymer, preferably a polyolefin, in the presence of a stabilizer mixture, wherein the stabilizer mixture is incorporated into the thermoplastic polymer or applied onto the thermoplastic polymer before or during processing of the thermoplastic polymer. The stabilizer mixture comprises at least two of the components selected from (i), (ii), and (iii), Here, Component (i) is a hydroxylamine or amine oxide; Component (ii) is benzofuran-2-one of formula (I). The component (iii) is chromanol, 【Chemistry 9】 During the ceremony, R ３ This is a substituted carbocyclic or heterocyclic aromatic ring system. R ４ , R ５ , R ６ and R ７ Each substituent is independently selected from hydrogen or chloro; hydroxy; a substituted or unsubstituted hydrocarbyl group optionally containing at least one heteroatom; a substituted or unsubstituted hydrocarbyloxy group optionally containing at least one further heteroatom; a substituted or unsubstituted cyclohydrocarbyl group optionally containing at least one heteroatom; or a hydrocarbylthio group optionally containing at least one further heteroatom. If the stabilizer mixture contains components (i), (ii), and / or (iii), then it is present in the composition in an amount of less than 500 ppm by total weight of components (i), (ii), and / or (iii) present in the stabilizer mixture, based on the weight of the thermoplastic polymer. If the stabilizer mixture contains components (ii) and (iii) without (i), it is present in the composition in an amount less than 300 ppm, preferably less than 250 ppm, preferably 200 ppm or less, more preferably 150 ppm or less, and even more preferably 100 ppm or less, based on the weight of the thermoplastic polymer.

13. The method according to claim 12, comprising any one of the features defined in any one of claims 2 to 11.

14. The method according to claim 12 or 13, wherein the stabilizer mixture is provided as a masterbatch.

15. The use of a stabilizer mixture to improve processability and / or reduce discoloration when processing thermoplastic polymers, preferably polyolefins, During the ceremony, The stabilizer mixture comprises at least two of the components selected from (i), (ii), and (iii), During the ceremony, Component (i) is a hydroxylamine or amine oxide; Component (ii) is benzofuran-2-one of formula (I); The component (iii) is chromanol, 【Chemistry 10】 During the ceremony, R ３ This is a substituted carbocyclic or heterocyclic aromatic ring system. R ４ , R ５ , R ６ and R ７ Each substituent is independently selected from hydrogen or chloro; hydroxy; a substituted or unsubstituted hydrocarbyl group optionally containing at least one heteroatom; a substituted or unsubstituted hydrocarbyloxy group optionally containing at least one further heteroatom; a substituted or unsubstituted cyclohydrocarbyl group optionally containing at least one heteroatom; or a hydrocarbylthio group optionally containing at least one further heteroatom. If the stabilizer mixture contains components (i), (ii), and / or (iii), then it is present in the composition in an amount of less than 500 ppm by total weight of components (i), (ii), and / or (iii) present in the stabilizer mixture, based on the weight of the thermoplastic polymer. If the stabilizer mixture contains components (ii) and (iii) without (i), it is used in an amount of less than 300 ppm, preferably less than 250 ppm, preferably 200 ppm or less, more preferably 150 ppm or less, and even more preferably 100 ppm or less, based on the weight of the thermoplastic polymer.

16. The use according to claim 15, comprising any of the features defined in claims 2 to 11 or claim 14.

17. A stabilizer mixture for processing thermoplastic polymers, preferably polyolefins, wherein the composition comprises component (i) and component (iii), and optionally component (ii). Here, Component (i) is a hydroxylamine or amine oxide; Component (ii) is benzofuran-2-one of formula (I); The component (iii) is chromanol, 【Chemistry 11】 During the ceremony, R ３ This is a substituted carbocyclic or heterocyclic aromatic ring system. R ４ , R ５ , R ６ and R ７ A stabilizer mixture in which each is independently of the others a substituent selected from hydrogen, chloro; hydroxy; a substituted or unsubstituted hydrocarbyl group optionally containing at least one heteroatom; a substituted or unsubstituted hydrocarbyloxy group optionally containing at least one further heteroatom; a substituted or unsubstituted cyclohydrocarbyl group optionally containing at least one heteroatom; or a substituent selected from hydrocarbylthio, optionally containing at least one further heteroatom.

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