EP4139388A1 - Use of hydroxycarboxylic acid salts for stabilizing thermoplastic condensation polymers, stabilized moulding compositions and moulding compositions produced therefrom - Google Patents

Abstract

The present invention relates to the use of hydroxycarboxylic acid salts for stabilising thermoplastic condensation polymers, a stabilised moulding composition and moulding compositions produced therefrom. The invention also relates to a method for stabilising thermoplastic condensation polymers and possible uses of the moulding composition.

Description

Use of hydroxycarboxylic acid salts for stabilizing thermoplastic condensation polymers, stabilized molding compounds and molding compounds and molded parts produced therefrom

The present invention relates to the use of hydroxycarboxylic acid salts for stabilizing thermoplastic condensation polymers, a stabilized molding composition and molded parts produced therefrom, a method for stabilizing thermoplastic condensation polymers and possible uses of the molding composition.

Condensation polymers such as polyester such as PET and polyamides such as PA-6 are important plastics for packaging and technical applications that are often intended for long-term use. Furthermore, today polymers based on polyester made from renewable raw materials such as PLA (polylactide) or PBS (polybutylene succinate) are seen as possible substitutes for oil-based plastics, especially in the packaging industry and for agricultural applications. However, these applications, e.g. in the form of foils, tend to have a short-term useful life. Regardless of the useful life, however, it is necessary that condensation polymers do not experience any (pre-) damage during processing, ie during the manufacture of parts or during compounding, in order not to prematurely lose properties such as mechanical properties to suffer.

For this purpose, additives such as stabilizers and / or antioxidants are often added to the polymers.

The stabilization of polyesters based on renewable raw materials has hitherto been carried out by customary phenolic antioxidants and / or phosphites such as, for example, in Meng, Xin; Shi, Guotao; Wu, Chushi; Chen, Weijie; Xin, Zhong; Shi, Yaoqi; Sheng, Yan (2016): Chain extension and oxidation stabilization of Triphenyl Phosphite (TPP) in PLA, Polymer Degradation and Stability 124, pp. 112-118, in Georgousopoulou, loanna-Nektaria; Vouyiouka, Stamatina; Dole, Patrice; Papaspyrides, Constantine D. (2016): Thermo-mechanical degradation and stabilization of poly (butylene succinate), Polymer Degradation and Stability 128, pp. 182-192 or in WO 2010000638 (Applicant: BASF SE). However, these solutions are not based on renewable raw materials, which is especially true for polymers that are already made from renewable resources Raw materials such as PLA and PBS would be desirable.

Hydroxycarboxylic acid salts are mentioned in the form of sodium citrate in CN 105838049 as additives to shape-memory polylactic acid composites, but as fillers in a series with other typical fillers such as calcium carbonate or talc and not as stabilizers.

In CN 101020780, sodium citrate is listed as a nucleating agent for polylactic acid wood composites in a list with various additives such as calcium carbonate, but not used as a stabilizer.

In CN 101362833 sodium citrate is used as a foam stabilizer in the production of polylactic acids within a list of coupling agents, but not as a polymer stabilizer.

JP 2006-328222 uses salts of hydroxycarboxylic acids to stabilize polyacetal / polylactic acid blends, but to reduce the splitting off of formaldehyde.

Furthermore, in JP H05-7179245, ester salts of hydroxycarboxylic acids are mentioned as stabilizers for various polymers.

There is no reference to the stabilizing effect in the processing of condensation products such as PLA or PBS in any of the above-mentioned publications.

The object of the present invention was therefore to develop stabilizers, in particular for stabilizing the processing of condensation polymers, which are effective, inexpensive, environmentally friendly and based on readily available raw materials. This object could be achieved with the stabilizers according to the invention with hydroxycarboxylic acid salts as stabilizing agents.

This object is achieved with regard to the use of at least one hydroxycarboxylic acid salt for stabilizing thermoplastic condensation polymers with the features of patent claim 1, with regard to a condensation polymer composition with the features of patent claim 11, with regard to a molding compound or a molded part with the features of claim 17, with regard to a method for oxidative, thermal and / or actinic stabilization of a thermoplastic condensation polymer with the features of claim 18 and with regard to uses of the condensation polymer compositions with the features of claim 20 solved. The respective dependent claims represent advantageous developments.

In a first aspect, the invention thus relates to the use of at least one hydroxycarboxylic acid salt for stabilizing thermoplastic condensation polymers, in particular against oxidative, thermal and / or actinic degradation.

Surprisingly, it was found that the use according to the invention of at least one hydroxycarboxylic acid salt allows the production and applications of thermoplastic condensation polymers, in particular from renewable raw materials such as polylactic acid (PLA), without premature loss of properties during processing.

It is essential for the stabilizing effect that the carboxylic acid salt contains a hydroxyl group, which means that the use according to the invention differs from conventional acid scavengers that do not have hydroxyl groups, such as calcium stearate. In terms of functionality, it is assumed that the hydroxyl group interrupts radical degradation mechanisms through hydrogen transfer, at the same time a neutral pH value can be maintained and a complex formation and thus deactivation of the oxidation-promoting metal ions can be postulated as a further effect.

A preferred embodiment provides that the thermal stabilization takes place during the thermal processing of the condensation polymers, in particular by adding, adding or incorporating the at least one hydroxycarboxylic acid salt to or into the thermoplastic condensation polymer.

An exemplary thermal processing of the condensation polymers can be, for example, processing in the thermoplastic state, where- when the condensation polymer is usually melted, preferably using a mixer, kneader or extruder. Preferred processing machines are extruders such as, for example, single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, which are preferably equipped with vacuum degassing. Processing can take place under air or, if necessary, under inert gas conditions. Here, the addition or incorporation of the at least one hydroxycarboxylic acid salt can take place during processing.

It is also possible to mix the at least one hydroxycarboxylic acid salt prior to thermal processing with the thermoplastic condensation polymers, which can be in the form of powder, granules, beads or chips, for example, and then to process the mixture in the thermoplastic state.

Thermal processing is preferably carried out under aprotic conditions. Aprotic conditions are understood to mean that compounds that can easily give off a proton, e.g. acids or water, are largely absent. In particular, aprotic conditions are characterized in that the thermoplastic condensation polymer has a maximum water content of up to 0.5% by weight, preferably up to 0.05% by weight.

Preferred hydroxycarboxylic acid salts are, for example, selected from the group consisting of alkali metal, alkaline earth metal, aluminum and zinc salts of hydroxycarboxylic acids, in particular hydroxycarboxylic acids selected from the group consisting of alpha-, beta-, gamma, delta or omega-hydroxycarboxylic acids , preferably linear or branched aliphatic or aromatic hydroxycarboxylic acid compounds with 2 to 34 carbon atoms and their derivatives (e.g. cyclic hydroxycarboxylic acid esters such as lactones, or anhydrides from which the hydroxycarboxylic acids can be obtained again, but also hydroxycarboxylic acids with a similar structure), in particular - dere hydroxye than acid (glycolic acid), D-, L-, DL-2-hydroxypropanoic acid (D-, L-, DL-lactic acid, 2-hydroxypropionic acid), 3-hydroxypropanoic acid (3-hydroxypropionic acid) , 2-hydroxybutanoic acid (2-hydroxybutyric acid), 3-hydroxybutanoic anic acid (3-hydroxybutanoic acid), 4-hydroxybutanoic acid (4-hydroxybutyric acid), hydroxypentanoic acid (hydroxy va leric acid), hydroxyhexanoic acid (hydroxy caproic acid), hydroxyheptanoic acid (hydroxyenanthic acid), hydroxy octanoic acid (hydroxy octanoic acid), (Hydroxy pe largic acid), Hydroxydecanoic acid (Hydroxyca pric acid), Hydroxyundecanoic acid, Hydroxydodecanoic acid (Hydroxylauric acid), Hydroxytrideca acid, Hydroxytetradecanoic acid (Hydroxymyristic acid), Hydroxypentadecanoic acid (hydroxymyristic acid), Hydroxypentadecanoic acid, Hydroxyheptadecanoic acid (hydroxy- margaric acid), hydroxyoctadecanoic acid (Hydroxystearic acid), Hydroxynonadecanoic acid, Hydroxyeicosanoic acid (Hydroxyacharinsäure), Hydroxyheneicosanoic acid, Hydroxydocosanoic acid (hydroxy-bezoic acid), hydroxy-acetanoic acid (hydroxy-bezoic acid), hydroxy-behenoic acid (hydroxy-behenoic acid), hydroxy-behenoic acid (hydroxy-behenoic acid), hydroxy-bezoic acid, hydroxy-behenoic acid (hydroxy-behenoic acid), hydroxy-behenoic acid, hydroxy-behenic acid, Hydroxycerotic acid), hydroxyheptacosanoic acid, hydroxyoctacosanoic acid (Hydroxymontansä ure), hydroxynonacosanoic acid, hydroxytriacontanoic acid (hydroxymelissinic acid), hydroxydotriacontanoic acid (hydroxylaccersic acid), hydroxytetratriacontanoic acid (hydroxygeddic acid), hydroxycarboxylic acids substituted with alkyl groups and / or carbonyl groups, such as 2-methyl-2-hydroxycarboxylic acids propanoic acid (2-hydroxy-isobutyric acid), 2-hydroxy-2-methyl-butyric acid, 3-hydroxy-3-methyl-butyric acid and 2-hydroxy-2-methyl-3-oxobutyric acid; D ihydroxy carbonic acids such as mevalonic acid and glyceric acid; Polyhydroxycarboxylic acids such as, for example, quinic acid, isosaccharic acid, lactobionic acid. Further suitable hydroxycarboxylic acids are aldonic acids such as aldotetronic acids, aldopentonic acids, aldohexonic acids, in particular gluconic acid, ribonic acid, arabinonic acid, xylonic acid, mannonic acid, galactonic acid, gulonic acid, ketoaldonic acids, uronic acids such as. Glucuronic acid, mannuronic acid, galacturonic acid and aldaric acids such as glucaric acid, xylaric acid, galactaric acid, gular acid; long-chain and unsaturated hydroxycarboxylic acids such as ricinoleic acid; aromatic hydroxycarboxylic acids such as mandelic acid, vanillin mandelic acid and dibasic or tri-basic hydroxycarboxylic acids such as malic acid, citric acid, isocitric acid or tartaric acid. Furthermore, oligosaccharides or polysaccharides which have carboxylic acid and hydroxyl groups in the repeating unit, such as, for example, polygalacturonic acid, polymannuronic acid, polyguluronic acid, and in particular alginic acid, for example according to the formula I, are preferred.

In the above formula, m ... and n each represent a number from 5-100

Sodium citrate (trisodium citrate), calcium citrate (tri-calcium dicitrate), sodium malate (disodium malate), calcium malate, sodium tartrate and sodium alginate are particularly preferred.

The forms of the salts listed which are free of water of crystallization are very particularly preferred. Salts which give off a maximum of 10% by weight of water of crystallization under the respective processing conditions are characterized as free of water of crystallization. This includes, in particular, salts which can be converted into this state by customary drying methods.

Based on the condensation polymer, the at least one hydroxycarboxylic acid salt is preferably used in a weight ratio of 0.01 to 10.00% by weight, preferably 0.05 to 5.00% by weight, particularly preferably from 0.10 to 1% by weight .-% used.

Exemplary condensation polymers are selected from the group consisting of

Polyesters from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids such as polylactic acid (PLA), polybutylene succinate, poly (butylene succinate-co-adipate), poly (butylene adipate) (PBA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polybutylene terephthalate , Polypropylene terephthalate (PPT), polyethylene furanoate (poly (ethylene-2,5-furandicarboxylate)) (PEF), polyethylene naphthylate, poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoate, polyhydroxynaphthalate, polycaprolactone (PCL), poly-3 hydroxybutyrate, poly-4-hydroxybutyrate, poly-3-hydroxyvalerate, poly (hexamethylene succinate), as well as copolymers and mixtures or blends of two or more more of the aforementioned polymers;

Polyamides such as PA 6, PA 6.6, PA 6.10, PA 4.6, PA 4.10, PA 6.12, PA 10.10, PA 10.12, PA 12.12, PA 11, PA 12; partially aromatic polyamides such as polyphthalamides, for example made from terephthalic acid and / or isophthalic acid and aliphatic diamines or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4 or 1,3-diaminobenzene;

Polycarbonates or polyester carbonates; and also mixtures, combinations or blends of two or more of the aforementioned polymers.

Preferred condensation polymers are aliphatic polyesters made from aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol and aliphatic dicarboxylic acids such as malonic acid , Succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, fumaric acid or itaconic acid as well as from hydroxycarboxylic acids or their ring-forming compounds such as polycaprolactone, poly-3-hydroxybutyrate, poly-4-hydroxybutyrate , Poly-3-hydroxyvalerate, poly (hexamethylene succinate), poly (butylene succinate), poly (butylene succinate-co-adipate), polylactic acid, very particularly preferred is polylactic acid (PLA).

The very particularly preferred polylactic acid (PLA) can be produced from L-lactide or D-lactide or a mixture L / D, usually by ring-opening polymerization of the lactide (dimer of lactic acid). PLA can also be in the form of a copolymer. Hydroxycarboxylic acids such as glycolic acid, 4-hydroxybutyric acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid or mandelic acid are preferably used as comonomers in PLA copolymers. In principle, copolymers of PLA obtained from a diol such as ethylene glycol or butanediol and an acid such as adipic acid or terephthalic acid are also possible. Copolymers can be in the form of statistical (“random”), block or “tapered” structures or as stereoblock copolymers.

In principle, the condensation polymers can contain additives of other thermoplastic polymers to a minor extent.

In a further aspect, the present invention relates to a condensation polymer composition containing or consisting of

A) at least one hydroxycarboxylic acid salt, as well as

B) at least one thermoplastic condensation polymer.

With regard to the hydroxycarboxylic acid salt, reference is made to the statements made above in connection with the use according to the invention, which also apply in full to the composition according to the invention.

The condensation polymer composition preferably contains or consists

(A) 0.01 to 10.00% by weight, preferably 0.05 to 5.00% by weight, particularly preferably from 0.10 to 1.00% by weight of the at least one hydroxycarboxylic acid salt,

(B) 90.00 to 99.99% by weight, preferably 95.00 to 99.95% by weight, particularly preferably 99.00 to 99.90% by weight, of at least one condensation polymer.

The condensation polymer composition according to the invention can additionally contain at least one additive which is preferably selected from the group consisting of primary antioxidants, secondary antioxidants with the exception of phosphites and phosphonites, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants , Nucleating agents, anti-nucleating agents, impact strength improvers, lubricants, rheology modifiers, thixotropic agents, chain extenders, processing aids, mold release agents, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, coupling agents, antiblocking agents, antistatic agents, coupling agents, antiblocking agents , Hydrophilizing agents, hydrophobizing agents, adhesion promoters, dispersants, compatibilizers, Oxygen scavengers, acid scavengers, propellants, breakdown additives, defoaming agents, odor scavengers, marking agents, anti-fogging agents and mixtures thereof.

Plasticizers, fibers such as glass fibers and / or carbon fibers and fillers are not included in the additives. In the event that plasticizers, fibers and / or fillers are contained in the condensation polymer composition, these substances in their total can contain up to 80 parts by weight, based on 100 parts by weight of the condensation polymer composition described above ( ie the sum of components (A) and (B)).

In a preferred embodiment, the compositions contain in particular further classes of nucleating agents, additives for increasing molecular weight (chain extenders) or fillers.

Preferred nucleating agents are talc, alkali or alkaline earth salts of mono- and polyfunctional carboxylic acids such as. B. benzoic acid, succinic acid, adipic acid, for example sodium benzoate, zinc glycerolate, aluminum hydroxy bis (4-tert-butyl) benzoate, 2,2'-methylenebis (4,6-di-tert-butylphenyl) ) phosphate, as well as trisamides and diamides such as trimesic acid tricyclohexylamide, trimesic acid tri (4-methylcyclohexylamide), trimesic acid tri (tert-butylamide), N, N ', N "-1,3,5-benzene triyltris (2,2-dimethyl- propanamide) or 2,6-naphthalenedicarboxylic acid dicyclohexylamide or orotic acid.

Preferred additives for increasing molecular weight (chain extenders) are diepoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-acyllactams, bis-maleimides, dicyanates, carbodiimides. Further suitable chain extenders are polymeric compounds such as polystyrene-polyacrylate-polyglycidyl (meth) acrylate copolymers, polystyrene-maleic anhydride copolymers and polyethylene-maleic anhydride copolymers.

Preferred fillers and / or reinforcing materials are calcium carbonate, silicates, talc, mica, kaolin, metal oxides and metal hydroxides, carbon black, graphite, wood flour or fibers from natural products such as cellulose, glass fibers, carbon fibers, polyaramid fibers and other synthetic polymer fibers. Further suitable fillers are flydrotalcite or zeolites or sheet silicates such as, for example, montmorillonite, bentonite, beidelite, mica, flectorite, saponite, vermiculite, ledikite, magadite, lllite, kaolinite, wollastonite, attapulgite.

Examples of further additives that the compositions according to the invention can additionally contain are primary and secondary antioxidants:

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

Suitable phenolic antioxidants are, for example:

Alkylated monophenols, such as, for example, 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di -tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol , 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols, such as 2,6-dinonyl- 4-methylphenol, 2,4-dimethyl-6- (1'-methylundec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) phenol and mixtures thereof;

Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol;

Flydroquinones and alkylated flydroquinones, such as, for example, 2,6-di-tert-butyl-4-methyoxyphenol, 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-hydroxylphenyl) adipate;

Tocopherols, such as, for example, α-, β-, γ-, δ-tocopherol and mixtures of these (vitamin E); Hydroxylated thiodiphenyl ethers, such as 2,2'-thiobis (6-tert-butyl-4-methyl- phenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3-methyl-phenol), 4,4'-thiobis (6-tert-butyl-2- methylphenol), 4,4'-thiobis (3,6-di-sec-amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide;

Alkylidenebisphenols, such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl- 6- (a-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclhexylphenol), 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 ' -Methylene bis [6- (a-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (a, a-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2 , 6-di-tert-butylphenol, 4,4'-methylenebis (6-tert-butyl-2-methyl-phenol), 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-dodecyl mercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hyd - roxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'- tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methyl-phenyl] terephthalate, 1,1-bis- (3,5-dimethyl-2-hydroxyphenyl) butane, 2, 2- bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecyl mercaptobutane, 1, 1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane;

O-, N- and S-benzyl compounds, such as, for example, 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercapto acetate , 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; Hydroxybenzylated malonates, such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, 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; Aromatic hydroxybenzyl compounds, such as, for example, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert -butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol;

Triazine compounds such as 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-hydroxphenylethyl) -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;

Benzyl phosphonates, such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl

3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of

3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid;

Acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate;

Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-flexandiol, 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-phospha-2,6,7-trioxabicyclo [2.2.2] octane;

Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-flexandiol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, Ne- opentyl 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-phosphomethyl -2,6,7-trioxabicyclo [2.2.2] octane, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] - 2,4,8,10-tetraoxaspiro [5.5] undecane;

Esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols, e.g. methanol, ethanol, octanol, octadecanol, 1,6-flexandiol, 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, trimethylolxymethyl- 1-phosphymethyl 2,6,7-trioxabicyclo [2.2.2] octane;

Esters of (3,5-di-tert-butyl-4-hydroxyphenyl) acetic acid with mono- or polyhydric alcohols, e.g. 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, trimethylhexenetadecanol , Trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane;

Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, such as N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamide, N, N ' - bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamide, 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, distributed by Uniroyal);

Ascorbic acid (vitamin C).

Particularly preferred phenolic antioxidants are the following structures:

Further particularly preferred phenolic antioxidants are based on renewable raw materials such as B. tocopherols (vitamin E), tocotrienols, tocomonoenols, carotenoids, hydroxytyrosol, flavonols such as chrysin, quercitin, hesperidin, neohesperidin, naringin, morin, kaempferol, fisetin, anthocyanins such as delphinidin and malvidin, curcumin, carnosolic acid and resveratrol.

Suitable aminic antioxidants are, 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-methyl-pentyl) -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-tolu - olsulfamoyl) diphenylamine, N, N'-dimethyl-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 diphenylamine, e.g. p, p'-di-tert-octyldiphenylamine, 4-n-buty-aminophenol, 4-butyrylaminophenol, 4- Nonanoylaminophenol, 4-dodec- canoylaminophenol, 4-octadecanoylamino-phenol, bis (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, N, N, N ', N'-Tetra-methyl-4,4'-diamino-diphenylmethane, 1,2-bis [(2-methyl-phenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-Octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyl-diphenylamines, a mixture of mono- and dialkylated tert- Butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl / tert-octylphenothiazines, a mixture of mono- and dialkylated tert- Octylphenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphs nyl-1,4-diaminobut-2-en and mixtures or combinations thereof.

Preferred amine antioxidants are: 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-phenylene-diamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine.

Further preferred aminic antioxidants are hydroxylamines or N-oxides (nitrones), such as, for example, N, N-dialkylhydroxylamines, N, N-dibenzylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-distearylhydroxylamine, N-benzyl-α-phe - nylnitron, N-octadecyl-α-hexadecylnitron, as well as Genox EP (additive) according to the formula:

R ₁ , R ₂ = C _{1 4} -C ₂₄ alkyl Suitable lactones are benzofuranones and indolinones such as, 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), 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert- butyl-benz-ofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,4-dimethylphenyl ) -5,7-di-tert-butyl-benzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one.

Suitable secondary antioxidants are organosulfur compounds such as sulfides and disulfides, e.g. distearyl thiodipropionate, dilauryl thiodipropionate; Ditridecyldithiopropionate, ditetradecylthiodipropionate, 3- (dodecylthio) -1,1 '- [2,2-bis [[3- (dodecylthio) -1-oxopropoxy] methyl] -1,3-propanediyl] propanoic acid ester.

Suitable light stabilizers are, for example, compounds based on 2- (2'-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides and 2- (2-hydroxyphenyl) -1,3,5-triazines.

Suitable 2- (2'-hydroxyphenyl) benzotriazoles are, for example, 2- (2'-hydroxy-5'methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole , 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-Di-tert-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, 2 - (3'-sec-Butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-Di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis (a, a-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl -2'-hydroxy-5 '- (2-octyloxycarbonyl-ethyl) 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' -t ert- 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-benzotriazol-2-ylphenol]; the product of the transesterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] - 2H-benzotriazole with polyethylene glycol 300; [R-CH ₂ CH ₂ - COO-CH ₂ CH ₂ -] - _2, wherein R = 3'-tert-butyl-4'-hydroxy-5' -2H-benzotriazol-2-ylphenyl, 2- [2'-hydroxy-3 '- (a, a-dimethylbenzyl) -5' - (1,1,3, 3-tetramethylbutyl) phenyl] benzotriazole, 2- [2'-hydroxy-3 '- (1,1,3,3-tetramethylbutyl) -5' - (a, a-dimethylbenzyl) phenyl] benzotriazole.

Suitable 2-hydroxybenzophenones are, 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 of 2-hydroxybenzophenones.

Suitable acrylates are, for example, ethyl α-cyano-β, β-diphenyl acrylate, iso-octyl-α-cyano-β, β-diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, Butyl α-cyano-β-methyl-p-methoxy-cinnamate, methyl-α-carbomethoxy-p-methoxycinnamate, and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline.

Suitable esters of benzoic acids are, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert- butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di- tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

Suitable oxamides are, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxy-oxanilide, 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 its mixtures 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.

Suitable 2- (2-hydroxyphenyl) -1,3,5-triazines are, for example, 2,4,6-T ris (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-dimethyl-phenyl) -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-hexyloxy) phenyl-4,6-diphenyl-

1.3.5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy -2-hydroxypropoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2 -Hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4-dimethylphenyl-

1.3.5-triazine.

Suitable metal deactivators are, for example, N, N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4- hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis- (benzylidene) oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbisphenylhydrazide, N, N'-diacetyladipoyldihydrazide, N, N'-N, N'-bis (salicyloyl) oxyrazide , N, N'-bis (salicyloyl) thiopropionyl dihydrazide.

Suitable hindered amines are, 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 -octy- loxy-2,2,6,6-tetramethyl-4-piperidyl) sebazate, bis (1, 2,2,6, 6-pentamethyl-4-piperidyl) -n-butyl-3,5-di- tert-butyl-4-hydroxybenzylmalonate, the condensation product of 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, 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, linear or cyclic condensation products from N, N'-bis (2,2,6,6-tetramethyl-4- piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-di-aza- 4-oxospiro- [4.5] decane and epichlorohydrin.

Oligomeric and polymeric hindered amines of the following structures are preferred:

In the case of the compounds mentioned above, n is in each case from 3 to 100. Suitable dispersants are, for example:

Polyacrylates, e.g. copolymers with long-chain side groups, polyacrylate block copolymers, alkylamides: e.g. N, N'-1,2-ethanediylbisoctadecanamide, sorbitan esters, e.g. monostearyl sorbitan esters, titanates and zirconates, reactive copolymers with functional groups e.g. polypropylene-co-acrylic acid, Polypropylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-alt-maleic anhydride-polysiloxanes: for example dimethylsilanediol-ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic copolymers: for example polyethylene-block-polyethylene oxide, dendrimers containing dendrimers, for example hydroxyl trimer groups .

Suitable anti-nucleating agents are azine dyes such as nigrosine.

Suitable flame retardants are, in particular, inorganic flame retardants such as Al (OH) ₃ , Mg (OH) ₂ , AIO (OH), MgCO ₃ , sheet silicates such as montmorillonite or sepiolite, unmodified or organically modified, double salts such as Mg-Al- Silicates, POSS (Polyhedral Oligomeric Silsesquioxane) compounds, huntite, hydromagnesite or halloysite

Suitable pigments can be inorganic or organic in nature. Inorganic pigments are, for example, titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, carbon black, organic pigments are, for example, anthraquinones, anthanthrones, benzimidazolones, quinacridones, diketopyrrolopyrroles, Dioxazines, indanthrones, isoindolinones, azo compounds, perylenes, phthalocyanines or pyranthrones. Further suitable pigments are effect pigments based on metal or pearlescent pigments based on metal oxide.

Suitable optical brighteners are, for example, bisbenzoxazoles, phenylcoumarins or bis (styryl) biphenyls and, in particular, optical brighteners of the formulas:

Suitable filler deactivators are, for example, polysiloxanes, polyacrylates, in particular block copolymers such as polymethacrylic acid-polyalkylene oxide or polyglycidyl (meth) acrylates and their copolymers, for example with styrene, and epoxides, for example of the following structures:

n = 1-10

Suitable antistatic agents are, for example, ethoxylated alkylamines, fatty acid esters, alkyl sulfonates and polymers such as polyether amides.

Suitable antiozonants are the above-mentioned amines, such as, for example, N, N'-diisopropyl-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, N-cyclohexyl-N'-phenyl-p-phenylenediamine

Suitable mold release agents are, for example, montan waxes.

The above-described additive composition and, if necessary, the additional additives are incorporated into the plastic or the condensation polymer by customary processing methods, the polymer being melted and mixed with the additive composition according to the invention and any further additives, preferably by mixers, kneading ter or extruder. Preferred processing machines are extruders such as single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, which are preferably equipped with vacuum degassing. Processing can take place under air or, if necessary, under inert gas conditions.

Furthermore, the additive compositions according to the invention can be used in In the form of so-called masterbatches or concentrates, which contain, for example, 10-90% by weight of the compositions according to the invention in a polymer, are produced and introduced.

The at least one additive is, based on 100 parts by weight of components (A) and (B), from 0.01 to 5.00% by weight, preferably from 0.05 to 3.00% by weight , particularly preferably from 0.10 to 1.00% by weight.

The present invention also relates to a molding compound or a molded part that can be produced or produced from the condensation polymer composition according to the invention, in particular in the form of foils (films), in particular agricultural foils such as mulch, tunnel or perforated foils, tapes ders, hollow bodies and foams, injection molded parts, fibers, profiles and other extrudates, parts from additive or generative manufacturing processes such as fused layer modeling (FLM), layer laminate modeling (LLM), selective laser sintering (SLS) and other 3D Printing processes, packaging for food or cosmetic products, encapsulation of active ingredients and biologically active substances, bandages, surgical sutures and / or hygiene products, in particular as a component of disposable diapers, sanitary towels and tampons.

The present invention also relates to a method for oxidative, thermal and / or actinic stabilization of a thermoplastic condensation polymer, in particular against oxidative, thermal and / or actinic degradation by adding, adding or incorporating at least one hydroxycarboxylic acid salt to or into the thermoplastic condensation polymer. With regard to the hydroxycarboxylic acid, reference is made to the statements above, which also apply in full to the process according to the invention.

The thermal stabilization preferably takes place during the thermal processing of the condensation polymers, the thermal processing taking place in particular under aprotic conditions.

The invention also relates to the use of a condensation polymer composition according to the invention - for the production of packaging, in particular packaging for food or cosmetic products;

- In the pharmaceutical industry, in particular for the encapsulation of active ingredients and biologically active substances;

- in medical technology, in particular for the production of bandages and surgical sutures;

- in hygiene products, in particular as part of disposable diapers, sanitary towels and tampons; and or

- in agricultural applications, e.g. for the production of agricultural films such as mulch, tunnel or perforated films.

The present invention is described in more detail with reference to the following exemplary embodiments, without restricting the invention to the specific parameters.

Embodiments:

As PLA were Luminy L 175 (≤ 0.5% of D-lactic acid according to certificate, MVR = 4.7 cm ^3/10 min measured at 190 ° C / 2.16 kg ram weight) (comparative examples game 1) and L Luminy 130 (≤ 0.5% D-lactic acid according to the certificate) (comparative example 2 and 3) from Corbion were used. Before processing, the polymers were dried in a vacuum drying cabinet at 80 ° C. for at least 16 h.

The inventive examples and the comparative examples were produced by extrusion with a co-rotating Process 11 twin-screw extruder from Thermo Fisher Scientific, with a screw diameter of 11 mm and a length to diameter ratio (L / D) of 40.

The additives were mixed manually with the matrix polymer in a plastic bag and dosed volumetrically. Processing took place at a throughput of 1 kg / h and a screw speed of 200 rpm at 200 ° C.

The MVR was measured on an MI-2 melt index tester from Göttfert at a test temperature of 190 ° C. and a punch weight of 2.16 kg. Before the measurement, the samples were for at least 16 h dried in a vacuum oven at 80 ° C. The preheating time was 4 minutes. Give reasonable is the MVR min in ^cm3 / 10 min.

Comparative example 4 and inventive examples 13 to 17

To further test the effect of the stabilizer composition according to the invention, a polylactide (PLA) Luminy L175, supplier: Total Corbion, was ground and dried for 16 hours at 80 ° C. in a vacuum oven together with the table below specified additives at 210 ° C in a twin screw microextruder (Micro 5cc, manufacturer DSM) in continuous mode at 150 revolutions per minute for 10 minutes in the melt in a circle. The force absorption is measured after 5 and 10 minutes. The force is a measure of the toughness of the melt and therefore of the molecular weight. The higher the remaining force, the lower the degradation of the polymer. The mean value from 2 tests is given in each case.

Tabel:

Analogously to Comparative Examples 4 and Examples 13 to 17 according to the invention, the residual force was determined after 30 minutes at 210 ° C. and 150 revolutions per minute:

Tabel AO = pentaerythritol tetrakis [3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionate

P = tris (2,4-di-tert-butylphenyl) phosphite

The addition of hydroxycarboxylic acid salts (examples according to the invention in the tables) demonstrates very good processing stability of the polymer due to a higher retention of force compared to the comparative examples, which can be further increased by antioxidants as in examples 17 and 18 according to the invention.

Claims

Claims

1. Use of at least one hydroxycarboxylic acid salt for stabilizing thermoplastic condensation polymers, in particular against oxidative, thermal and / or actinic degradation.

2. Use according to claim 1, characterized in that the thermal stabilization takes place during the thermal processing of the condensation polymers, in particular by adding, adding or incorporating the at least one hydroxycarboxylic acid salt to or into the thermoplastic condensation polymer.

3. Use according to the preceding claim, characterized in that the thermal processing takes place under aprotic conditions.

4. Use according to one of the preceding claims, characterized in that the at least one Hydroxyca rbo nsä u resa Iz is an inorganic hydroxycarboxylic acid salt and is in particular selected from the group consisting of alkali metal, alkaline earth metal, aluminum and zinc salts of Hydroxy Carbo nic Acid, whereby the at least one Hydroxy Carbo nic Acid is used, especially in its anhydrous form.

5. Use according to one of the preceding claims, characterized in that the hydroxycarboxylic acid is selected from the group consisting of alpha-, beta-, gamma, delta or omega-hydroxycarboxylic acids, preferably linear or branched aliphatic or aromatic hydroxycarboxylic acid compounds with 2 to 34 carbon atoms and their derivatives (e.g. cyclic hydroxycarboxylic acid esters such as lactones, or anhydrides from which the hydroxycarboxylic acids can be obtained again, but also hydroxycarboxylic acids ren with a similar structure), in particular hydroxyethanoic acid (glycolic acid), D-, L-, DL-2-hydroxypropionic acid (D-, L-, DL-lactic acid, 2-hydroxypropionic acid), 3-hydroxypropionic acid (3-hydroxypropionic acid ), 2-Hydroxybutanoic acid (2-Hydroxybutyric acid), 3-Hydroxybutanoic acid (3-Hydroxybutyric acid), 4-Hydroxybutanoic acid (4-Hydroxybutyric acid), Hydroxypentaic acid (Hydroxy va leric acid), Hydroxyhexanoic acid (H yd roxyca pronic acid), hydroxyheptanoic acid (hydroxyönantanthic acid), hydroxyocta nic acid (hydroxycaprylic acid), hydroxynonanoic acid (hydroxypelargonic acid), hydroxydecanoic acid (hydroxycapric acid), hydroxy nanoic acid, hydroxydecanoic acid, hydroxydodecanoic acid re, hydroxytetradecanoic acid (hydroxymyristic acid), hyd roxy pe ntadeca n acid, hydroxyhexadecanoic acid (hydroxypalmitic acid), hydroxyheptadecanoic acid (hydroxymargaric acid), hydroxyoctadeca nic acid, hydroxy-acyanic acid (hydroxy-acyanic acid), hydroxynonic acid neocosanic acid, hydroxydocosanic acid (hydroxybehenic acid), hydroxyltricosanoic acid, hydroxytetra cosaic acid (hydroxylignoceric acid), hydroxypentacosanoic acid, hydroxyhexacosanoic acid (hydroxycerotic acid, hydroxyma- tic acid - acid), hydroxynonacosanoic acid, hydroxytriacontanoic acid (hydroxymelissinic acid), hydroxyd ot ri a co nta n acid (hydroxyllaccersic acid), hydroxytetratriacontanoic acid (hydroxydeddic acid), with alkyl groups and / or carbonyl group-substituted hydroxycarboxylic acids such as 2 Hydroxy-2-methyl-propanoic acid (2-hydroxy-isobutyric acid), 2-hydroxy-2-methyl-butyric acid, 3-hydroxy-3-methyl-butyric acid and 2-hydroxy-2-methyl-3-oxobutyric acid; D ihyd roxycar bo n acids such as mevalonic acid and glyceric acid; Polyhydroxycarboxylic acids, such as, for example, quinic acid, isosaccharic acid, lactobionic acid, sugar acids, in particular aldonic acids, such as, for example, aldotetronic acids, aldopentonic acids, aldohexonic acids, in particular gluconic acid, ribonic acid, arabinonic acid, xylonic acid, mannonic acid, galactonic acid, gulonic acid; Uronic acids such as glucuronic acid mannuronic acid, galacturonic acid and aldaric acids such as glucaric acid, xylaric acid, galactaric acid, gular acid; long-chain and unsaturated hydroxycarboxylic acids such as ricinoleic acid; aromatic hydroxycarboxylic acids such as mandelic acid, vanillin-mandelic acid, dibasic or tri-basic hydroxycarboxylic acids such as malic acid, citric acid, isocitric acid or tartaric acid, and oligosaccharides or polysaccharides that have carboxylic and hydroxyl groups in the repeating unit, such as polygalacturonic acid, polygalacturonic acid, and especially alginic acid.

6. Use according to one of the preceding claims, characterized in that the at least one hydroxycarboxylic acid salt is selected from the group consisting of sodium citrate (trisodium citrate), calcium citrate (tricalcium dicitrate), sodium malate (disodium malate), calcium malate, sodium tartrate and sodium alginate.

7. Use according to one of the preceding claims, characterized in that the at least one hydroxycarboxylic acid salt, based on the condensation polymer, is in a weight ratio of 0.01 to 10.00% by weight, preferably 0.05 to 5.00 % By weight, particularly preferably from 0.10 to 1.00% by weight, is used.

8. Use according to one of the preceding claims, characterized in that the condensation polymer is selected from the group consisting of

Polyesters made from aliphatic or aromatic dicarboxylic acids and diols or from hydroxycarboxylic acids, preferably aliphatic polyesters such as, for example, polylactic acid (PLA), polybutylene succinate, poly (butylene succinate-co-adipate), poly (butylene adipate) (PBA), polyethylene terephthalate (PET) ), Polybutylene terephthalate (PBT), polypropylene terephthalate (PPT), polyethylene furanoate (poly (ethylene-2,5-furandicarboxylate)) (PEF), polyethylene naphthylate, poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoate, polyhydroxynaphthalone-, polycaprolone 3-hydroxybutyrate, poly-4-hydroxybutyrate, poly-3-hydroxyvalerate, poly (hexamethylene succinate), poly (butylene succinate) and copolymers and mixtures or blends of two or more of the aforementioned polymers;

Polycarbonates or polyester carbonates; Polyamides such as PA 6, PA 6.6, PA 6.10, PA 4.6, PA 4.10, PA 6.12, PA 10.10, PA 10.12, PA 12.12, PA 11, PA 12; partially aromatic polyamides such as polyphthalamides, for example made from terephthalic acid and / or isophthalic acid and aliphatic diamines or from aliphatic dicarboxylic acids such as adipic acid or sebacic acid and aromatic diamines such as 1,4- or 1,3-diaminobenzene; and also mixtures, combinations or blends of two or more of the aforementioned polymers.

9. Use according to one of the preceding claims, characterized in that the condensation polymer is selected from the group consisting of aliphatic polyesters such as PLA, PBA and copolymers thereof, the PLA copolymers preferably by ring-opening polymerization of D-lactide and / or L Lactide with comonomers selected from hydroxycarboxylic acids, in particular glycolic acid, 4-hydroxybutyric acid, 3-hydroxybutyric acid, 3-hydroxyvaleric acid or mandelic acid; Diols, especially ethylene glycol or butanediol; and / or carboxylic acids, in particular adipic acid or terephthalic acid; can be obtained.

10. Use according to one of the preceding claims, characterized in that the hydroxycarboxylic acid salt is an inorganic citrate and the thermoplastic condensation polymer is selected from the group consisting of aliphatic polyesters.

11. Condensation polymer composition containing or consisting of

A) at least one hydroxycarboxylic acid salt, as well as

B) at least one thermoplastic condensation polymer.

12. Condensation polymer composition according to the preceding claim, characterized in that the condensation polymer composition (A) 0.01 to 10.00% by weight, preferably 0.05 to 5.00% by weight, particularly preferably 0.10 to 1.00% by weight of the at least one hydroxycarboxylic acid salt,

(B) contains or contains from 90.00 to 99.99% by weight, preferably from 95.00 to 99.95% by weight, particularly preferably from 99.00 to 99.90% by weight, of at least one condensation polymer consists of this.

13. Condensation polymer composition according to claim 11 or 12, characterized in that the condensation polymer composition, in addition to components (A) and (B), contains at least one additive selected from the group consisting of primary Antioxidants, secondary antioxidants with the exception of phosphites and phosphonites, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, anti-nucleating agents, impact strength improvers, lubricants, rheology modifiers, flame retardants, processing aids, demolding agents, chain extenders , Dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anti-crosslinking agents, hydrophilizing agents, hydrophobizing agents, adhesion promoters, dispersants, compatibilizers ators, oxygen scavengers, acid scavengers, blowing agents, degradation additives, defoaming agents, odor scavengers, marking agents, anti-fogging agents and mixtures thereof.

14. Condensation polymer composition according to one of claims 11 to 13, characterized in that based on 100 parts by weight of components (A) and (B) up to 80 parts by weight, preferably 0.1 to 60 parts by weight. Parts, particularly preferably 1 to 50 parts by weight. At least one plasticizer, filler and / or reinforcing material is included.

15. condensation polymer composition according to one of claims 13 to 14, characterized in that the i) Degradation additives are selected from the group consisting of organic transition metal compounds such as, for example, transition metal carboxylates, in particular iron (III) stearate and / or manganese (II) stearate; ii) plasticizers are selected from the group consisting of tributyl acetyl citrate, tributyl citrate, triethyl citrate, triethyl acetyl citrate, glycerol triacetate, epoxidized soybean oil and / or epoxidized linseed oil; iii) nucleating agents are selected from the group consisting of talc, alkali metal or alkaline earth metal salts of mono- and polyfunctional carboxylic acids, in particular of benzoic acid, succinic acid, adipic acid, for example sodium benzoate and aluminum hydroxy-bis (4-tert-butyl) benzoate; Zinc glycerolate, 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate, trisamides and diamides such as trimesic acid tricyclohexylamide, trimesic acid tri (4-methylcyclohexylamide), trimesic acid tri (tert-butyl amide) , N, N ', N "-1,3,5-Benzoltriyltris (2,2-dimethyl-propanamide), 2,6-Naphthalenedicarbosäuredicyclohexylamid and / or orotic acid; iv) chain extenders are selected from the group consisting of diepoxides, Bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-acyllactams, bis-maleimides, dicyanates, carbodiimides and / or polymeric chain extenders, for example polystyrene-polyacrylate-polyglycidyl (meth) acrylate Copolymers, polystyrene-maleic anhydride copolymers and polyethylene-maleic anhydride copolymers; v) fillers and / or reinforcing materials are selected from the group consisting of calcium carbonates, silicates, talc, mica, kaolins, metal oxides, metal hydroxides, carbon black, graphite , Wood flour, fibers from natural products such as cellulose loose, glass fibers, carbon fibers, polyaramid fibers and other synthetic polymer fibers, hydrotalcites, zeolites and / or phyllosilicates such as montmorillonite, bentonite, Beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, lllite, kaolinite, wollastonite, attapulgite.

16. Condensation polymer composition according to one of claims 11 to 15, characterized in that the at least one additive, based on 100 parts by weight of components (A) and (B), amounts to 0.01 to 5.00 % By weight, preferably 0.05 to 3.00% by weight, particularly preferably from 0.10 to 1.00% by weight.

17. Molding compound or molded part producible from a condensation polymer composition according to one of claims 11 to 16, in particular in the form of foils (films), in particular agricultural foils such as mulch, tunnel or perforated foils, tapes, hollow bodies and foams , Injection molded parts, fibers, profiles and other extruded data, parts from additive or generative manufacturing processes, such as fused layer modeling (FLM), layer laminate modeling (LLM), selective laser sintering (SLS) and other 3D printing processes, Packaging for food or cosmetic products, encapsulations of active ingredients and biologically active substances, bandages, surgical sutures and / or hygiene products, in particular as a component of disposable diapers, sanitary towels and tampons.

18. Process for the oxidative, thermal and / or actinic stabilization of a thermoplastic condensation polymer, in particular against oxidative, thermal and / or actinic degradation by adding, adding or incorporating at least one hydroxycarboxylic acid to or into the thermoplastic condensation polymer .

19. The method according to the preceding claim, characterized in that the thermal stabilization takes place during the thermal processing of the condensation polymers, the thermal processing taking place in particular under aprotic conditions.

20. Use of the condensation polymer composition according to one of claims 11 to 16 - for the production of packaging, in particular packaging for food or cosmetic products;

- in the pharmaceutical industry, especially for the encapsulation of active ingredients and other biologically active substances; - in medical technology, in particular for the production of bandages and surgical suture material; and or

- in hygiene products, in particular as a component of disposable diapers, sanitary towels and tampons;

- in agricultural applications, e.g. for the production of agricultural films such as mulch, tunnel or perforated films.