Method for hydrolyzing condensed polymers and use of additive compositions

Abstract

The present invention relates to an additive composition comprising at least one hydroxycarboxylic acid salt and at least one organophosphorus compound, which composition can promote the hydrolysis of thermoplastic condensation polymers during use by incorporating the additive composition. The present invention further relates to a condensation polymer composition to which the additive composition of the present invention has been added. The present invention further relates to a method for the hydrolytic degradation of thermoplastic condensation polymers, and uses of the additive composition and thermoplastic condensation polymer composition of the present invention.

Description

Technical Field

[0001] The present invention relates to an additive composition comprising at least one hydroxycarboxylate and at least one organic phosphorus compound. The composition can promote the hydrolysis of a thermoplastic condensation polymer in which the additive composition is blended. Furthermore, the present invention relates to a condensation polymer composition to which the additive composition according to the present invention is added. Furthermore, the present invention relates to a method for hydrolyzing a thermoplastic condensation polymer and the use of the additive composition and the thermoplastic condensation polymer composition according to the present invention.

Background Art

[0002] Condensation polymers such as polyesters such as PET (Polyethylene terephthalate) and polyamides such as PA-6 (Polyamide-6) are important plastics for packaging and technical applications, and are often intended for long-term use. Furthermore, polyester-based polymers formed from renewable raw materials such as PLA (polylactide) and PBS (polybutylene succinate) are considered today to be potential alternatives to petroleum-based plastics, especially in the packaging industry and agricultural applications. However, in these applications, for example in the form of films, the service life tends to be short. However, regardless of the service life, it is necessary for condensation polymers not to be (previously) damaged during the manufacture or formulation of parts. For example, it is necessary to prevent characteristics such as mechanical properties from being lost prematurely. For this purpose, additives such as stabilizers and antioxidants are often added to the polymer.

[0003] Various possibilities have been described for promoting the degradation of condensation polymers, especially polylactic acid. For example, degradation can be accelerated by using specific microorganisms (W. Pattanasuttichonlakul et al., International Biodeterioration and Biodegradation 2018, 132, 74-83) or enzymes (WO2005 / 063037), or by using specific environmental conditions.

[0004] Other possibilities include adding degradation-promoting additives such as TiO2 nanoparticles (Y. Luo et al. J. Appl. Pol. Sci. 2018, 46509, 1-8) or silica nanoparticles (P. Georgiopoulus et al. Journal of Biomaterials Applications 2014, 29, 662-674) or oxidation-promoting additives such as manganese stearate (CN103408827) to achieve photocatalytic degradation.

[0005] Furthermore, methods are known to influence the degradation of PLA by adding inorganic substances such as MgO and ZnO (US20140360728) or organic fillers such as chitosan and keratin (MAElsawy et al. Renewable and Sustainable Energy Reviews 2017, 79, 1346-1352).

[0006] Furthermore, PLA blends combining PLA with quickly degradable polymers, such as a mixture of polybutylene succinate (Y. Wang et al. Polym. Bull. 2016, 73, 1067-1083), have been described.

[0007] Known methods for accelerating degradation either involve using them only after the plastic parts are manufactured (microorganisms, enzymes), fundamentally altering the degradation properties (photochemical or oxidative), or fundamentally altering the material properties (fillers, blends). However, acidic or basic environments during processing are counterproductive, as they cause significant damage to the polymer.

[0008] Hydroxycarboxylic acids are listed in CN105838049 in the form of sodium citrate as an additive for shape-memory polylactic acid composite materials, but they are listed as fillers alongside other typical fillers such as calcium carbonate and talc, and are not listed as stabilizers.

[0009] In CN101020780, sodium citrate, in particular, is listed as a nucleating agent in polylactic acid and wood composites, along with various additives such as calcium carbonate, but it is not used as a stabilizer.

[0010] In CN101362833, sodium citrate is listed as a foam stabilizer in the production of polylactic acid as a coupling agent, but it is not used as a polymer stabilizer.

[0011] Japanese Patent Publication No. 2006-328222 describes how a hydroxycarboxylic acid salt is used to stabilize a polyacetal / polylactic acid mixture and reduce formaldehyde cleavage.

[0012] Furthermore, Japanese Patent Publication No. 05-7179245 describes ester salts of hydroxycarboxylic acids as stabilizers for various polymers. [Overview of the Initiative] [Problems that the invention aims to solve]

[0013] Therefore, the object of the present invention was, on the one hand, to develop an additive composition that enables the processing of condensed polymers with little to no prior damage, that is, to act stabilizingly in the thermoplastic processing of condensed polymers, and on the other hand, to promote or control hydrolysis in the environment as needed. [Means for solving the problem]

[0014] The present objective is achieved with respect to an additive composition for promoting the hydrolysis and decomposition of a thermoplastic condensation polymer having the characteristics of claim 1, a condensation polymer composition having the characteristics of claim 11, a molded compound or molded part having the characteristics of claim 20, a method for hydrolyzing and decomposing a condensation polymer having the characteristics of claim 21, the use of an additive composition having the characteristics of claim 22, and the use of a condensation polymer composition having the characteristics of claim 23. The dependent claims show a favorable development.

[0015] Therefore, in the first aspect, the present invention, a) at least one hydroxycarboxylate salt, b) at least one organophosphorus compound, This relates to an additive composition containing or consisting of the following. Surprisingly, it was found that the additive composition according to the present invention enables the production of a condensation polymer composition in which hydrolysis is promoted in the aforementioned environment without prematurely losing its physical properties during manufacturing. [Modes for carrying out the invention]

[0016] For example, the additive composition according to the present invention can be incorporated into a condensed polymer composition during the heat treatment of the condensed polymer. In particular, the additive composition according to the present invention can be incorporated into a thermoplastic condensed polymer by addition, supplementation, or incorporation.

[0017] For example, a typical thermal processing of a condensation polymer is processing in a thermoplastic state, in which the condensation polymer is generally melted by, preferably, a mixer, a kneader or an extruder. For example, extruders equipped with a vacuum degassing mechanism, such as single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, etc., are preferred as processing machines. Here, the processing may be carried out in air or, as an option, under inert gas conditions. Here, the addition or incorporation of the additive composition can be carried out during processing.

[0018] Also, the additive composition may be mixed with the thermoplastic condensation polymer before the heat treatment. The thermoplastic condensation polymer can exist, for example, in the form of chips, powders, beads or pellets. Also, thereafter, it is possible to process the mixture in a thermoplastic state.

[0019] The thermal processing is preferably carried out under aprotic conditions. The expression "under aprotic conditions" is understood to mean, for example, the absence of compounds that can easily donate protons, such as acids and water. In particular, the aprotic conditions may be characterized in that the water content of the thermoplastic condensation polymer is 0.5 wt% or less, and preferably characterized in that it is 0.05 wt% or less. Therefore, it is also preferable that the additive according to the present invention exists in an anhydrous form.

[0020] Here too, it is essential that the carboxylate contains a hydroxy group. Therefore, it is different from the uses according to the invention of conventional acid scavengers that do not contain a hydroxy group, such as calcium stearate. The operating principle is that the hydroxyl group inhibits the radical decomposition mechanism via hydrogen transfer while simultaneously maintaining a neutral or stable pH value, and a further effect is hypothesized: complexation with oxidation-promoting metal ions.

[0021] For example, hydroxycarboxylate salts are alkali metal salts of hydroxycarboxylic acids, alkaline earth kind It is preferable to select from the group consisting of metal salts, aluminum salts, and zinc salts. In particular, hydroxycarboxylic acids are α, β, γ, δ, or ω hydroxycarboxylic acids, preferably linear or branched aliphatic or aromatic hydroxycarboxylic acid compounds and their derivatives having 2 to 34 carbon atoms (e.g., cyclic hydroxycarboxylic acid esters such as lactones, or anhydrides from which hydroxycarboxylic acids can be obtained again, hydroxycarboxylic acids of similar structure, etc.), in particular hydroxyethane acid (glycolic acid), D-,L-,DL-2-hydroxypropanoic acid (D-,L-,D-L-lactic acid, 2-hydroxypropionic acid, 3-hydroxypropanoic acid, 2-hydroxybutanoic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, hydroxypentanoic acid, hydroxyhexanoic acid, hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxynonanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, hydroxydodecanoic acid, hydroxytetradecanoic acid, hydroxypentadecanoic acid, hydroxyhexadecanoic acid, hydroxyheptadecanoic acid, hydroxyoctadecanoic acid, hydroxynonadecanoic acid, hydroxyeicosanoic acid, hydroxyheneicosanoic acid, hydroxydocosanoic acid, hydroxytricosanoic acid, hydroxytetracosanoic acid, hydroxypentacosanoic acid, hydroxyhexacosanoic acid, hydroxyheptacosanoic acid, hydroxyoctacosanoic acid, hydroxynonacosanoic acid, hydroxytriacontanoic acid, hydroxydotriacontanoic acid, hydroxytetratriacontanoic acid, for example, 2-hydroxy-2-methyl-propanoic acid, 2-hydroxy-2-methyl-butanoic acid, 3-hydroxy-3-methyl-butanoic acid, 2-hydroxy-2-methyl-3-oxobutanoic acid and other hydroxycarboxylic acids modified by an alkyl group and / or a carbonyl group; for example, dihydroxycarboxylic acids such as mevalonic acid and glyceric acid; for example, polyhydroxycarboxylic acids such as quinic acid, isosaccharinic acid, lactobionic acid and the like are preferably selected from the group consisting of., Further suitable hydroxycarboxylic acids include, for example, aldotetronic acid, aldopentonic acid, aldohexonic acid, and other aldonic acids, particularly gluconic acid, ribonic acid, arabinonic acid, xylonic acid, mannonic acid, galactonic acid, and guronic acid; ketoaldonic acids, for example, glucuronic acid, mannuronic acid, and galacturonic acid; aldalic acids, for example, glucaric acid, xylaneic acid, galactaric acid, and gularic acid; long-chain unsaturated hydroxycarboxylic acids, for example, ricinoleic acid; aromatic hydroxycarboxylic acids, for example, mandelic acid and vanillin-mandelic acid; and dibasic or tribasic hydroxycarboxylic acids, for example, malic acid, citric acid, isocitric acid, and tartaric acid. Furthermore, oligosaccharides or polysaccharides having carboxylic acid and hydroxyl groups in repeating units, such as polygalacturonic acid, polymanuronic acid, polyguluronic acid, and especially alginic acid as shown in the formula below, are also preferred.

[0022] [ka]

[0023] Particularly preferred are sodium citrate (trisodium citrate), calcium citrate (tricalcium citrate), sodium malate (disodium malate), calcium malate, sodium tartrate, and sodium alginate.

[0024] Salts that do not contain water molecules in their crystal structure are particularly preferred. Here, a salt that does not contain water molecules in its crystal structure is considered to be a salt that loses up to 10% by weight of water molecules in its crystal structure under specific processing conditions. This includes certain salts that can be converted to this state by everyday drying methods.

[0025] The organophosphorus compound is preferably hydrolyzable and contains at least one, preferably two, and particularly preferably three ester groups. The hydrolysis stability of phosphoric acid esters depends on the specific alcohol structure. Aromatic polyesters, i.e., phenol derivatives and sterically hindered structures, have higher hydrolysis resistance compared to aliphatic structures, i.e., alcohol derivatives. The organophosphorus compound preferably contains at least one, more preferably at least two, and especially preferably three aliphatic ester groups per P atom. Furthermore, linear ester groups, i.e., groups with low steric hindrance, are particularly preferred.

[0026] In a more preferred embodiment, the organophosphorus compound is selected from the group consisting of phosphite compounds having one, two, or three linear or branched alkoxy groups. Furthermore, phosphite compounds are [ka] (However, R 1 From the number of carbon atoms: 3 Selected from the group consisting of 6 linear or branched alkyl groups and aryl groups, R 1 (These may be the same or different), and P(OR 1 )Equation 3 (where R 1 The compound is preferably selected from the group consisting of linear or branched alkyl groups having 4 to 32 carbon atoms, particularly trilauryl phosphate, triisodecyl phosphate, tridecyl phosphate, trihexadecyl phosphate, trioctadecyl phosphate, tribehenyl phosphate, trialaxidyl phosphate, triceryl phosphate, trioleyl phosphate, tris(2-ethylhexyl) phosphate, for example monostearyl phosphate phosphite (or its tautomer monostearyl phosphonic acid), distearyl phosphate (distearyl phosphonic acid), and other diphosphates and polymer congeners, partially esterified phosphonic acid compounds, and their alkali salts, alkaline earth salts, aluminum salts or zinc salts. Examples of phosphates include tetraethyl phosphate and tetrapropyl phosphate. An example of triphosphate is P,P'-bis(2-hydroxyethyl) ester of triphosphoric acid. Oligophosphites and polyphosphites (oligomers and polymer phosphites) are described, for example, in International Publication No. 2011 / 102861, International Publication No. 2014 / 20519, International Publication No. 2020 / 123986, etc. Compounds described in these publications are also included in the present invention. Examples of compounds include the following:

[0027] [ka]

[0028] Furthermore, the materials also include, for example, phosphate esters, diphosphate esters, metaphosphate esters, polyphosphate esters derived from the aforementioned phosphite esters, such as trilauryl phosphate, triisodecyl phosphate, tridecyl phosphate, trihexadecyl phosphate, trioctadecyl phosphate, tribehenyl phosphate, trialaxidyl phosphate, triceryl phosphate, and trioleyl phosphate, as well as the following structures and salts derived therefrom, and mixtures of at least two phosphate esters selected from the group consisting of monoalkyl phosphate esters, dialkyl phosphate esters, and trialkyl phosphate esters.

[0029] [ka]

[0030] In the case of the aforementioned phosphite ester derivatives, such as the phosphate esters, diphosphate esters, metaphosphate esters, and polyphosphate esters, the phosphorus atom exists with an oxidation state of +V, rather than +III as in phosphite esters.

[0031] The organophosphorus compound is very preferably a phosphate salt, and is preferably selected from the group consisting of the following compounds.

[0032] [ka]

[0033] [ka]

[0034] The following compounds are preferred phosphonites that can be used for the purposes of the present invention.

[0035] [ka]

[0036] In a more preferred embodiment, the total amount of at least one hydroxycarboxylate salt and the total amount of at least one organophosphorus compound are present in a weight ratio of 20:1 to 1:20, preferably 10:1 to 1:10, and particularly preferably 5:1 to 1:5.

[0037] In a further aspect, the present invention is (A) at least one condensed polymer, (B) an additive composition according to one of the previous claims, This invention relates to a condensation polymer composition containing or comprising the following. In a more preferred embodiment, the condensation polymer may be, for example, polylactic acid (PLA), polybutylene succinate, polybutylene succinate-co-adipate, polybutylene adipate (PBA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene furanoate (polyethylene-2,5-lanedicarboxylic acid ester, PEF), polypropylene terephthalate (PPT), polyethylene naphthylate, poly-1,4-dimethylcyclohexane terephthalate, polyhydroxybenzoic acid, polyhydroxynaphthalate, polycaprolactone (PCL), poly-3-hydroxybutyric acid, poly-4-hydroxybutyric acid, poly-3-hydroxyvaleric acid, polyhexamethylene succinate, polybutylene succinate, etc. The materials preferably include polyesters of aliphatic or aromatic dicarboxylic acids and diols, or hydroxycarboxylic acids, copolymers, and mixtures of these polymers; for example, polyamides such as PA6, PA6.6, PA6.10, PA4.6, PA4.10, PA6.12, PA10.10, PA10.12, PA12.12, PA11, PA12; semi-aromatic polyamides such as polyphthalamide prepared from terephthalic acid and / or isophthalic acid and aliphatic diamines, such as adipic acid and sebacic acid, or aromatic diamines, such as 1,4-diaminebenzene and 1,3-diaminebenzene; polycarbonates or polyester carbonates; and mixtures, or combinations or mixtures of two or more of the above polymers.

[0038] Preferred condensation polymers include, for example, polyesters obtained from ethylene glycol, aliphatic diols such as 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol, and aliphatic carboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, fumaric acid, and itaconic acid, such as polycaprolactone, poly-3-hydroxybutyric acid, poly-4-hydroxybutyric acid, poly-3-hydroxyvaleric acid, polyhexamethylene succinic acid, polybutylene succinic acid, polysuccinate butylene-co-adipate, polylactic acid, or cyclic compounds.

[0039] In particular, the condensation polymer is selected from the group consisting of PLA, PBA, and copolymers thereof. However, the PLA copolymer is preferably obtained by ring-opening polymerization of D-lactide and / or L-lactide with a comonomer. The comonomer is preferably selected from particularly glycolic acid and hydroxycarboxylic acids such as 4-hydroxybutanoic acid, 3-hydroxybutanoic acid, 3-hydroxyvaleric acid, or mandelic acid; particularly diols such as ethylene glycol and butanediol; and particularly carboxylic acids such as adipic acid and terephthalic acid.

[0040] In the composition of the condensed polymer according to the present invention, the additive composition is contained in an amount of 0.01 to 10.00% by weight, preferably 0.05 to 5.00% by weight, and particularly preferably 0.10 to 2.00% by weight, relative to the composition of the total condensed polymer.

[0041] The condensation polymer composition according to the present invention may further contain at least one additive. The additive is selected from the group consisting of primary antioxidants, secondary antioxidants, UV absorbers, light stabilizers, metal deactivators, filler deactivators, ozone degradation inhibitors, nucleating agents, nucleating inhibitors, toughening agents, lubricants, rheology modifiers, thixotropes, chain extenders, processing aids, mold release agents, flame retardants, pigments, dyes, optical whitening agents, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anticrosslinking agents, hydrophilic agents, hydrophobic agents, hydrolysis stabilizers, binders, dispersants, compatibilizers, oxygen scavengers, acid scavengers, expanding agents, decomposition additives, defoaming agents, odor scavengers, marking agents, and anti-fogging agents.

[0042] Here, the total condensed polymer composition may contain at least one additive in an amount of 0.01 to 5.00% by weight, preferably 0.05 to 3.00% by weight, and particularly preferably 0.10 to 1.00% by weight.

[0043] Note that plasticizers, fibers such as glass fibers and carbon fibers, and fillers are not included in the additives. If plasticizers, fibers, and / or fillers are included in the condensed polymer composition, these substances may be included in amounts up to 80 parts by weight per 100 parts by weight of the above-mentioned condensed polymer composition.

[0044] In preferred embodiments, the composition particularly includes further types of nucleating agents, additives for increasing molecular weight (chain extenders), or fillers.

[0045] Preferred nucleating agents include talc, such as sodium benzoate, zinc glycerate, aluminum hydroxy-bis(4-tert-butyl)benzoic acid, 2,2-methylene-bis-(4,6-di-tert-butylphenyl) phosphoric acid, and salts of alkali metals or alkaline earth metals with carboxylic acids such as benzoic acid, succinic acid, or adipic acid, such as tricyclohexylamide trimesic acid, tri(4-methylcyclohexylamide trimesic acid), tri(tert-butylamide) trimesic acid, N,N',N”-1,3,5-benzoyltriyltris(2,2-dimethyl-propanamide), 2,6-naphthalenedicarboxylic acid cyclohexylamide, or diamides and triamides such as orotic acid.

[0046] Preferred additives (chain extenders) for increasing molecular weight include diexoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-acyllactams, bis-maleimides, dicyanates, and carbodiimides. More suitable chain extenders include polymer compounds such as polystyrene-polyacrylic acid-polymethacrylate glycidyl copolymer, polystyrene-maleic anhydride copolymer, and polyethylene-maleic anhydride copolymer.

[0047] Preferred fillers and / or reinforcing materials include calcium carbonate, silicates, talc, mica, kaolin, metal oxides, metal hydroxides, black carbon, graphite, wood flour, natural fibers such as cellulose, glass fibers, carbon fibers, polyaramid fibers, and other synthetic polymer fibers. More suitable fillers include hydrotalcite, zeolites such as montmorillonite, and phyllosilicates such as bentonite, bydelite, mica, hectorite, saponite, vermiculite, reddikite, magadite, illite, kaolinite, wollastonite, and attapulgite.

[0048] Further examples of additives that may be included in the composition according to the present invention are primary antioxidants and secondary antioxidants.

[0049] Suitable primary antioxidants (A) are phenolic antioxidants, amines, and lactones.

[0050] Suitable phenolic antioxidants include: For example, alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, and 2,6-di-tert-butyl-4-methoxymethylphenol; For example, linear or branched nonylphenols such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundecyl)phenol, 4-dimethyl-6-(1'-methylheptadecyl)phenol, and 2,4-dimethyl-6-(1'-methyltridecyl)phenol, and mixtures thereof; For example, alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, and 2,6-didodecylthiomethyl-4-nonylphenol; For example, hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, and bis(3,5-di-tert-butyl-4-hydroxylphenyl) adipate, as well as alkylated hydroquinones; For example, tocopherols such as α-, β-, γ-, δ-tocopherol and mixtures thereof (vitamin E); For example, hydroxylated thiodiphenyl ethers such as 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), and 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide; For example, 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-(α-methylcyclohexyl)phenol), 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-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3- tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol-bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3'-ter Alkylidene bisphenols such as t-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, and 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane; For example, O-, N-, and S-benzyl compounds such as 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, and isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate; For example, hydroxybenzylated malonic acid esters such as 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, and bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate; For example, aromatic hydroxybenzyl compounds such as 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, and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol; For example, 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-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 Triazine compounds such as -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, and 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate; For example, benzylphosphonic acid esters such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, dioctadecyl-3,5-di-tert-butyl-4-hydroxy-3-methylbenzylphosphonic acid, and calcium salts of monoethyl esters of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid; For example, acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearalanilide, and octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate; Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phosphate-2, and 6,7-trioxabicyclo[2.2.2]octane; β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid, and for example methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl) Esters of monohydric or polyhydric alcohols such as roxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phosphate-2, 6,7-trioxabicyclo[2.2.2]octane, and 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propynyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane; β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid, and for example methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, Esters of monohydric or polyhydric alcohols such as N,N'-bis(hydroxyethyl)oxamide, 3-thiaundadecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phosphate-2, and 6,7-trioxabicyclo[2.2.2]octane; Esters of (3,5-di-tert-butyl-4-hydroxyphenyl)acetic 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, 4-hydroxymethyl-1-phosphate-2, and 6,7-trioxabicyclo[2.2.2]octane; TIFF0007884459000009.tif37168

[0051] The most favored phenolic antioxidants have the following structure.

[0052] [ka]

[0053] [ka]

[0054] Furthermore, it is particularly preferable that the phenolic antioxidants are based on renewable raw materials such as tocotrienols, tocomonoenols, carotenoids, tocopherols (vitamin E) such as hydroxytyrosol, chrysin, quercetin, hesperidin, neohesperidin, naringin, morin, kaempferol, and fisetin, anthocyanins such as delphinidin and malvidin, curcumin, carnosolic acid, carnosol, rosmarinic acid, and resveratrol.

[0055] Suitable amine antioxidants include, for example, 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, 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'-di Methyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamines such as p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminopheno Lu, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetra-methyl-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-octyl 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 / isohexyl-diphenylamine, mixtures of mono- and dialkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, Phenothiazines, mixtures of mono- and dialkylated tert-butyl / tert-octylphenothiazines, mono- and dialkylated tert-octylphenothiazines, Examples include N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobuto-2-ene, and mixtures or combinations thereof.

[0056] Preferred amine antioxidants include N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, and N,N'-dicyclohexyl-p-phenylenediamine. Examples include didiamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, and N-cyclohexyl-N'-phenyl-p-phenylenediamine.

[0057] Further preferred amine antioxidants include, for example, hydroxylamines or N-oxides (nitrones) such as N,N-dialkylhydroxylamine, N,N-dibenzylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-distearylhydroxylamine, N-benzyl-α-phenylnitrone, N-octadecyl-α-hexadecylnitrone, and Genox EP (Addivant, registered trademark) as shown in the formula below. [ka]

[0058] Suitable lactones include, for example, 3-(4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-(2-hydroxyethoxy]phenyl)benzofuran-2-one), and 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one. Examples include benzofuranones and indolinones such as 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, and 3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one.

[0059] Suitable secondary antioxidants include, for example, organic sulfur compounds such as sulfides and disulfides, such as distearyl thiodipropionate, dilauryl thiodipropionate, ditridecyl dithiopropionate, ditetradecyl thiodipropionate, and 3-(dodecylthio)-1,1'-[2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]-1,3-propanediyl] propionic acid.

[0060] Suitable light stabilizers include, for example, compounds based on 2-(2'-hydroxyphenyl)benzotriazole, 2-hydroxybenzophenone, benzoic acid esters, acrylic acid esters, oxamides, and 2-(2'-hydroxyphenyl)-1,3,5-triazines. Suitable 2-(2'-hydroxyphenyl)benzotriazoles include, for example, 2-(2'-hydroxy-5'methylphenyl)benzotriazole, 2-(3',5'-di-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'-hydroxy-phenyl)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'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'methylphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonyl) Bonylethyl)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,Examples include [3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the product of the transesterification reaction of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; 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, or [R-CH2CH2-COO-CH2CH2-]-2, where R is 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazole-2-ylphenyl.

[0061] A suitable 2-hydroxybenzophenone is 2-hydroxybenzophenone Examples include 4-hydroxy-, 4-methoxy-, 4-octyloxy-, 4-decyloxy-4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy-, and 2'-hydroxy-4,4'-dimethyloxy derivatives.

[0062] Suitable acrylic acid esters include, for example, ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, Examples include α-cyano-β-methyl-p-methoxycinnamate butyl, α-carbomethoxy-p-methoxycinnamate methyl, and N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

[0063] Suitable benzoic acid esters include, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, Examples include 3,5-di-tert-butyl-4-hydroxybenzoate 2,4-di-tert-butylphenyl, 3,5-di-tert-butyl-4-hydroxybenzoate hexadecyl, 3,5-di-tert-butyl-4-hydroxybenzoate octadecyl, and 3,5-di-tert-butyl-4-hydroxybenzoate 2-methyl-4,6-di-tert-butylphenyl.

[0064] Suitable oxamides include, for example, 4,4'-dioctyloxyoxanilide. Examples include 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, mixtures of these with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of these with o- and p-methoxy-disubstituted oxanilides, and mixtures of these with o- and p-ethoxy-disubstituted oxanilides.

[0065] Suitable 2-(2-hydroxyphenyl)-1,3,5-triazines include, for example, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine. Liazine, 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-octyloxypropoxy)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-hex (Trioxy)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,Examples include 4-dimethylphenyl-1,3,5-triazine.

[0066] Suitable metal deactivators include, for example, N,N'-diphenyloxamide, N-salisilal-N'-salicyylhydrazine, N,N'-bis(salisiloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salisiloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl-bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salisiloyl)oxylyl dihydrazide, and N,N'-bis(salisiloyl)thiopropionyl dihydrazide.

[0067] Suitable hindered amines include, for example, 1,1-bis(2,2,6,6-tetramethyl-4-piperidyl) succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, and n-butyl(3,5-di-tert-butyl-4-hydroxybenzyl) malonate bis(1,2 Condensation products of ,2,6,6-pentamethyl-4-piperidyl), 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, nitrilol Tris(2,2,6,6-tetramethyl-4-piperidyl) triacetate, 1,2,3,4-butanetetracarboxylic acid tetrakis(2,2,6,6-tetramethyl-4-piperidyl), 1,1'-(1,2-ethanediyl)-bis(3,3,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethyl Examples include piperidine, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, and reaction products of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin.

[0068] The following structures are preferred as oligomers and polymer hindered amines.

[0069] [ka]

[0070] [ka] However, in the above compounds, n represents values ​​from 3 to 100.

[0071] Suitable dispersants include, for example, polyacrylic acid esters such as copolymers with long side chains or block copolymers of polyacrylic acid esters, alkylamides such as N,N'-1,2-ethanediylbisoctadecaneamide, sorbitan esters such as monostearylsorbitan ester, titanates, and zirconates, reactive copolymers having functional groups such as polypropylene-co-acrylic acid, polypropylene-co-maleic anhydride, and polyethylene-co-glycidyl methacrylate, polystyrene-alt-maleic anhydride-polysiloxanes such as dimethylsilanediol-ethylene oxide copolymer and polyphenylsiloxane copolymer, amphiphilic copolymers such as polyethylene block polyethylene oxide, and dendrimers such as dendrimers containing hydroxyl groups.

[0072] Suitable antinuclear-forming agents include, for example, azine dyes such as nigrosine.

[0073] Suitable flame retardants include, in particular, inorganic flame retardants such as Al(OH)3, Mg(OH)2, AlO(OH), and MgCO3; phyllosilicates such as montmorillonite and sepiolite; and unmodified or organically modified double salts such as Mg-Al silicates, POSS (polyhedral oligomer silsesquioxane) compounds, hunthite, hydromagnesite, or halloysite.

[0074] Suitable pigments may be inorganic or organic. Examples of inorganic pigments include titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, and black carbon. Examples of organic pigments include anthraquinones, antantrons, benzimidazolons, quinacridones, diketopyrrolopyrroles, dioxazines, indanthrenes, isoindolines, azo compounds, perylenes, phthalocyanines, or pyrantrons. Further suitable pigments include metal-based effect pigments and metal oxide-based pearl gloss pigments.

[0075] Suitable optical whitening agents include, for example, bis-benzoxazole, phenylcoumarin, or bis(styryl)biphenyl, and in particular, optical whitening agents represented by the following formula.

[0076] [ka]

[0077] Suitable filler deactivators include, for example, polysiloxanes, polyacrylic acid esters, particularly polymethacrylate-polyalkylene oxides, and block copolymers such as polyglycidyl (meth)acrylate, styrene, epoxides, and copolymers thereof. Examples of copolymer structures include the following:

[0078] [ka]

[0079] Suitable antistatic agents include polymers such as ethoxylated alkylamines, fatty acid esters, alkyl sulfonates, and polyetheramides.

[0080] Suitable anti-ozone agents include, for example, amines such as N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, and N-cyclohexyl-N'-phenyl-p-phenylenediamine.

[0081] Suitable release agents include, for example, montan wax.

[0082] The additive composition according to the present invention and optionally added additives are incorporated into the plastic by a conventional processing method. Here, the polymer is preferably melted by a mixer, kneader or extruder and mixed with the additive composition according to the present invention and optionally added additives. The processing machine is preferably an extruder equipped with a vacuum degassing mechanism, such as a single-screw extruder, twin-screw extruder, planetary roller extruder, ring extruder or co-kneader. Here, the processing may be carried out in air or optionally under inert gas conditions.

[0083] Furthermore, the additive compositions according to the present invention can be included, produced, and introduced in the form of so-called masterbatches or concentrates, for example, in which 10 to 90% of the composition according to the present invention is contained in a polymer.

[0084] The present invention further relates to molded compounds or molded parts manufactured or produced from condensation polymer compositions according to the present invention, particularly in the form of films, especially agricultural films such as mulch films, tunnel films or perforated films, tapes, hollow bodies, and foams, injection molded parts, fibers, profiles, and other extruded products, such as molten layer modeling (FLM) and This invention relates to molded parts manufactured by 3D printing such as layered laminate modeling (LLM) and selective laser sintering (SLS), as well as generative processing, packaging for food or cosmetics, encapsulation of surfactants and bioactive substances, dressings, surgical sutures and / or sanitary products, particularly disposable diapers, sanitary towels and tampons.

[0085] In a further embodiment, the present invention relates to a method for hydrolyzing a condensed polymer, comprising adding the additive composition according to the present invention to the condensed polymer and subjecting the added composition to hydrolysis conditions. Hydrolysis conditions are provided when the plastic composition comes into contact with water, for example, high air humidity, especially above 30%, sewage treatment plants where waste is composted, or generally environments such as rivers and oceans.

[0086] The present invention further relates to using the above-mentioned additive composition according to the present invention to accelerate the hydrolysis of a condensed polymer to which the additive composition has been added, compared to a condensed polymer to which the additive composition has been added, when the condensed polymer to which the additive composition has been added is subjected to hydrolysis conditions.

[0087] A particular advantage here is that the use of the additive composition according to the present invention enables the processing stabilization of the thermoplastic polymer in which it is incorporated under aprotic conditions, and at the same time, promotes the hydrolysis of the condensed polymer under protic conditions in specific applications.

[0088] The present invention further relates to the use of a condensation polymer composition according to one of the claims, For the manufacture of packaging, especially food or cosmetic packaging; In the pharmaceutical industry, particularly for encapsulating active ingredients and biologically active substances; In medical technology, particularly for the manufacture of dressings and surgical sutures; As an ingredient in sanitary products, especially disposable diapers, sanitary towels, and tampons; and / or, For example, its use in the manufacture of agricultural films such as mulch films, tunnel films, or perforated films. [Examples]

[0089] The present invention will be described in more detail with reference to the following examples, without limiting it to specific parameters.

[0090] Corbion's Luminy L175 (according to the certificate, D-lactic acid content is 0.5% or less, and the MVR measured at 190°C with a stamp weight of 2.16 kg is 4.7 cm) 3 PLA was used (10 mins). The polymer was dried in a vacuum drying cabinet at 80°C for at least 16 hours before processing.

[0091] The examples and comparative examples of the present invention were manufactured by extrusion using Thermo Scientific's "Process 11" parallel twin-thread extruder, with a thread diameter of 11 mm and a length-to-diameter ratio (LD) of 40.

[0092] The additives were manually mixed with the matrix polymer in a polybag and administered in volume units. Processing was carried out at 200°C with a throughput of 1 kg / h and a screw speed of 200 rpm.

[0093] To investigate the hydrolysis rate, the polymer was stored as pellets in deionized water at 35°C and 58°C, and the molecular weight variation (MVR) was measured after various time intervals.

[0094] TIFF0007884459000017.tif14168

[0095] [Table 1] [Table 2]

[0096] Weston 618F (manufactured by SI Group), which has the following structure, was used as the phosphite ester.

[0097] [ka]

[0098] The combination of hydroxycarboxylate salt and phosphorus compound used in the examples of the present invention allows for control and management of the degradability of PLA under protic conditions, depending on the ratio of the two components. When the phosphorus compound is in excess of or equal to the hydroxycarboxylate, degradation is accelerated, resulting in good processing stability (Examples 1 and 2 according to the present invention showed increased MVR after immersion in water compared to the comparative example). However, if degradation is to be slowed down, this can be achieved by using an excess amount of hydroxycarboxylate salt (Example 3 according to the present invention). Since the hydrolysis of the condensed polymer can be controlled by the ratio of hydroxycarboxylate salt to phosphate, it can be adjusted according to the application.

Claims

1. A method for hydrolyzing a condensed polymer selected from the group consisting of aliphatic or aromatic dicarboxylic acids and diols, or hydroxycarboxylic acids or their cyclic esters or diesters, a) At least one hydroxycarboxylate salt selected from the group consisting of sodium citrate (trisodium citrate), calcium citrate (tricalcium citrate), sodium malate (disodium malate), calcium malate, sodium tartrate, and sodium alginate, and b) [Chemical formula 1] Here, R １ These are identical or distinct organophosphorus compounds selected from the group consisting of linear or branched alkyl groups and aryl groups having 1 to 36 carbon atoms, An additive composition containing or comprising is added to a condensed polymer, and the added composition is exposed to hydrolysis conditions. The total amount of the at least one hydroxycarboxylate salt and the total amount of the at least one organophosphorus compound are used in a weight ratio of 5:1 to 1:

5. The additive composition is contained in the above composition in an amount of 0.10 to 2.00% by weight. method.

2. The use of additive compositions, a) At least one hydroxycarboxylate salt selected from the group consisting of sodium citrate (trisodium citrate), calcium citrate (tricalcium citrate), sodium malate (disodium malate), calcium malate, sodium tartrate, and sodium alginate, and b) [Chemical formula 2] Here, R １ These are identical or distinct organophosphorus compounds selected from the group consisting of linear or branched alkyl groups and aryl groups having 1 to 36 carbon atoms, An additive composition containing or comprising is added to a condensed polymer, and the added composition is exposed to hydrolysis conditions. The total amount of the at least one hydroxycarboxylate salt and the total amount of the at least one organophosphorus compound are used in a weight ratio of 5:1 to 1:

5. The additive composition is contained in the above composition in an amount of 0.10 to 2.00% by weight. When a condensed polymer selected from the group consisting of aliphatic or aromatic dicarboxylic acids and diols, or hydroxycarboxylic acids or their cyclic or diester esters, is exposed to hydrolysis conditions, the hydrolysis of the condensed polymer with the additive is accelerated compared to that of a condensed polymer without the additive. use.

3. The at least one hydroxycarboxylate salt is used in an anhydrous form. The method according to claim 1.

4. The at least one hydroxycarboxylate salt is used in an anhydrous form, The use described in claim 2.

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