WO2007138095A1 - Use of stabilizing compositions containing cyanine cations in packaging materials - Google Patents

Abstract

The present invention relates to the use of packaging materials containing a stabilizer composition, which, in turn, consists of (A) at least one stabilizer from at least a cyanine cation Cya<SUP>+</SUP> and at least one corresponding anion equivalent <SUP>1</SUP>/<SUB>m</SUB> An<SUP>m-</SUP>, and (B) at least one CO stabilizer chosen from boronate salts, sulfonium salts, iodide salts, sulfones, peroxides, pyridine N-oxides, and halogen methyltriazines, to protect the products packaged therein from the damaging effects of oxygen, light, and/or heat.

Description

Use of cyanine cation-containing stabilizer compositions in packaging materials

description

The present invention relates to the use of packaging materials containing a composition of cyanine cations and at least one co-stabilizer commonly used as a photoinitiator. This composition is hereinafter referred to as a stabilizer composition due to its use and serves to protect packaged products from the harmful action of oxygen and / or light and / or heat.

It is known that the mechanical, chemical and / or aesthetic properties of inanimate organic material under the action of energy, for. As oxygen and / or light and / or heat deteriorates. The consequence is an irreversible deterioration of the chemical and / or physical properties of the inanimate organic material. Also packaged products are subject to the action of oxygen and / or light and / or heat, which may result in damage to the mechanical, chemical, olfactory, gustatory, and / or aesthetic properties of these packaged products. The negative change manifests itself, depending on the packaged contents, in various ways, for example in a change in appearance, such as yellowing and discoloration, in a change in the taste and / or smell and / or in the breakdown of ingredients. For food, perfumes and cosmetic products, the shelf life can be greatly reduced. Typically, aging is due to oxidation reactions that can be triggered by heat, light, mechanical stress, catalysis, or by reaction with impurities. In order to reduce the decrease of the mechanical properties and the discoloration of the products, it is therefore customary to add to plastics substances that prevent or slow down damage. These substances are generally referred to as stabilizers. Numerous stabilizers are known for plastics.

Cyanine dyes are usually ionic, d. H. they consist of a cyanine cation and a corresponding anion. Usually, they are produced in their preparation as simple salts, for example as halides, tetrafluoroborates, perchlorates or tosylates.

Cyanine dyes and their preparation are known in principle, for example from DE 3721850, and have been proposed for a very wide variety of applications. For example, WO 05085372 describes compounds which absorb in the near infrared region of the electromagnetic spectrum (NIR absorber) consisting of a cyanine cation and a corresponding cation, and their use in offset and high-pressure inks.

EP 408 322 describes one-component photoinitiators in the form of the salts of cyanine dye and certain borane ions.

Also known are one-component photoinitiator systems in which cyanine, xanthylium or thiazine dyes are used as cation and a boranate compound as anion, see e.g. EP 223 587.

The unpublished German patent application DE 102004058584.9 describes the use of two-component NIR photoinitiator systems which contain at least one sensitizer and at least one co-initiator, as well as their use for free radical curing of coating compositions and other formulations.

The use of cyanine dyes in combination with co-stabilizers to protect organic matter is not yet known.

US 20030151025 describes oxygen barrier layers of polyethers or polyesters in combination with transition metal catalysts and an energy absorbing compound. The energy absorbing compound is activated by microwaves or a photoinitiator is used.

US 2005092963 provides as oxygen scavenger a hydrocarbon polymer containing a transition metal complex as a catalyst and a benzophenone-type photoinitiator. In addition, the side of the film made therefrom which faces the material to be protected is treated with a peroxide solution.

US 2005148680 describes a mixture for trapping oxygen from an ethylene homo- or co-polymer, a transition metal catalyst and a mixture of at least two photoinitiators. The photoinitiators used are benzophenones, thioxanthones, acylphosphine derivatives or diphenylsulfides.

WO 0236437 describes methods and systems for producing films as oxygen barrier layers, wherein the effect is initiated by the use of UV radiation. WO 9851759 describes an oxidizable compound which is reacted by UV irradiation of transition metal complexes. As photoinitiators, benzophenone derivatives are used.

WO 0236670 discloses the use of transition metal catalysts as oxygen scavengers. Preferably, these are used as stearates and acrylates.

From DE 19730498 and DE 19648256 compositions are known, which are prepared from the separate salts of a cationic dye and Boranatsalzen and can also be used in mixtures with UV photoinitiators.

The stabilizers known from the prior art have a number of disadvantages. A major disadvantage is the often too short duration of the protective effect.

It is an object of the present invention to provide stabilizers for packaging materials which are suitable for the protection of products packaged therein from the damaging effect of oxygen and / or light and / or heat, preferably over an extended period of time.

Surprisingly, it has now been found that the use of a packaging material containing at least one of the stabilizer compositions defined below is suitable for protecting articles which are sensitive to the action of oxygen and / or light and / or heat, the products to be protected at least partially being suitable surrounds with this packaging material.

The invention therefore relates to the use of a packaging material comprising a stabilizer composition comprising (A) at least one stabilizer of at least one cyanine cation Cya ⁺ and at least one corresponding anion equivalent ¹ / _m An ^{m "} , wherein the cyanine cation is selected among compounds of the general formulas (I), (II), (III), (IV), (V) or (VI),

wherein

n is 1 or 2; p is 0, 1, 2 or 3;

R ¹ and R ^{2 are} independently linear or branched, optionally substituted CrC ₂ o-alkyl radicals;

R ³ and R ^{4 are} independently H, CF ₃ or CN;

R ⁵ for each repeating unit is independently selected from hydrogen, halogen, phenyl, phenyloxy, phenylthio, diphenylamino, pyridyl, a barbituric acid or dimedone radical, where the phenyl and pyridyl radicals may optionally be substituted; R ⁶ for each repeat unit is independently selected from H, CF ₃ or CN;

R ^{7 is} a hydrogen, halogen, phenyl, phenyloxy, phenylthio, diphenylamino, pyridyl, a barbituric acid or a dimedone radical, where the phenyl and pyridyl radicals may optionally be substituted;

R ⁸ and R ^{9 are} independently C (CH ₃ ) ₂ , oxygen, sulfur, NR ^a, or -CH = CH-, where R ^{a is} a linear or branched, optionally substituted, CrC ₂ o-alkyl radical;

R ¹ , R ", R ¹ ", R ^ιv , R ^v , R ^vι , R ^v ", R ^vι ", R ^ιx , R ^x , R ^xι and R ^x "independently selected one or more, similar or different substituents among hydrogen, halogen, NO ₂ , CN, alkyl, alkoxy, SO ₂ CF ₃ , aryl or aryloxy;

and wherein the anion An ^{m "is} selected from halides, pseudohalides or anions of the general formula [AR ¹⁰ _k ] ^m" , in which

A is a polar ionic group;

R ^{10 is} at least one nonpolar group which is independently selected from C ₆ -C ₃₀ -alkenyl groups, C ₆ -C ₃₀ -cycloalkyl groups and (C ₃ -C ₃₀ -alkyl) aryl groups; k is 1, 2 or 3; m is 1 or 2; and

(B) at least one co-stabilizer selected from alkyl-substituted boranate salts, sulfonium salts, iodonium salts, sulfones, peroxides, pyridine-N-oxides and halomethyltriazines,

for the protection of packaged products from the harmful effects of oxygen and / or light and / or heat.

Particularly suitable for the use according to the invention are those of the stabilizer compositions described above, in which the co-stabilizer (B) is replaced by a compound of the formula (VII)

and an associated counterion ¹ / _x Kat ^{x +} , in which

x is 1 or 2;

Kat is an x-valent cation; z ¹ , z ² , z ³ and z ⁴ are each independently 0 or 1, the sum z ¹ + z ² + z ³ + z ^{4 being} 0, 1, 2 or 3; Y ¹ , Y ² , Y ³ and Y ⁴ are each independently O, S or NR ¹⁷ ;

R ¹³ , R ¹⁴ , R ¹⁵ and R ^{16 are} each independently selected from optionally substituted C 1 -C 18 -alkyl, optionally substituted C 2 -C 18 -alkyl, represented by one or more heteroatoms or heteroatom-containing groups selected from O, S , and NR ^b , wherein R ^{b is} alkyl, cycloalkyl or aryl, is interrupted, optionally substituted C 6 -C 14 -aryl, optionally substituted C 5 -C 12 -cycloalkyl, and optionally substituted five- to six-membered heterocycloalkyl and / or heteroaryl radicals ; and

R ¹⁷ is hydrogen, Ci-Cis-alkyl, _C6-Ci2 cycloalkyl, or C ₆ -C ₄ aryl;

with the proviso that at least one of the radicals R ¹³ to R ^{16 is} an optionally substituted C 1 -C 6 -alkyl radical and at least one of the radicals R ¹³ to R ^{16 is} an optionally substituted C 6 -C 14 -aryl radical, where said radicals may be optionally substituted ,

The term packaging materials is broadly understood in the context of the present invention and includes all forms of packaging, such as those used for wrapping materials for packaging, packaging, transporting, offering for sale, etc. These may be partially or completely dimensionally stable containers or products adapted to the shape of the packaged material, such as films. The packaging materials may partially or completely surround the packaged product. At least part of the packaging material contains a stabilizer composition according to the invention. Also included are combinations of several materials, eg. B. from a cardboard part and a film part, wherein z. B. only the film part contains a stabilizer composition according to the invention. The stabilizer compositions used according to the invention are particularly suitable for the protection of packaged products against the damaging effect of oxygen, in particular in combination with light and / or heat.

The stabilizer compositions used according to the invention are advantageously suitable for protection in non-living organic material of packaged products. They counteract undesirable oxygenation-induced aging and destruction of the products packaged in packaging material containing such stabilizer compositions.

In the following, the term "alkyl" encompasses straight-chain or branched hydrocarbon radicals having 1 to 500 carbon atoms (C 1 -C 5 -oalkyl). They are preferably straight-chain or branched C 1 -C 30 -alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl. Butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl, 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1 Ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2- Dimethylbutyl, 3,3-dimethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3 Heptyl, 2-ethylpentyl,

1-propylbutyl, n-octyl, 2-ethylhexyl, 2-propylheptyl, 1,1,3,3-tetramethylbutyl, nonyl, decyl, n-undecyl, n-dodecyl, n-tridecyl, isotridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl.

The term "alkyl" also includes alkyl whose carbon chain is replaced by one or more, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, nonadjacent groups selected from -O -, -S-, -NR ^a - (wherein R ^{a is} hydrogen or Ci-Cio-alkyl), -CO- and / or -SO 2 - may be interrupted, ie the termini of the alkyl group are formed by carbon atoms.

The term "alkyl" also includes substituted alkyl groups which generally have 1, 2, 3, 4, 5, 6, 7 or 8, preferably 1, 2, 3 or 4, and more preferably 1 or 2 substituents Substituents on alkyl are hydroxyl, halogen, cycloalkyl, aryl, heteroaryl, heterocyclyl, alkoxycarbonyl, COOR ^b , where R ^{b is} hydrogen or a metal ion equivalent and NR ^c R ^d , wherein R ^c and R ^{d are} independently hydrogen, cycloalkyl, aryl , Heteroaryl or heterocyclyl. The term "alkoxy" represents an alkyl group as mentioned above which is bonded via the oxygen atom (-O-), for example C 1 -C 10 -alkoxy, for example methoxy, ethoxy or propoxy.

The term "cycloalkyl" in the context of the present invention comprises an unsubstituted or substituted monocyclic or bicyclic saturated hydrocarbon group having generally 3 to 6, 8, 10, 12 or 15 carbon ring members, such as C 3 -C 15 -cycloalkyl, for example cyclopropyl, cyclobutyl, Cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or C7-Ci2-bicycloalkyl. In the case of a substitution, the cycloalkyl group may carry one or more, for example one, two, three, four or five substituents. Suitable substituents include alkyl, alkylcarbonyl, alkoxycarbonyl, hydroxy, alkoxy, alkylsulfanyl, NR ^c R ^d , wherein R ^c and R ^{d have} the meanings given above, and halogen.

The term "aryl" in the context of the present invention comprises a mono-, di- or trinuclear aromatic ring system containing 6 to 14 carbon ring members, which may be unsubstituted or substituted, for. Phenyl, naphthyl and anthracenyl. Preference is given to a mono- or binuclear ring system such as phenyl or naphthyl, more preferably a mononuclear aromatic ring system, phenyl.

In the case of a substitution, the aryl group may generally carry 1, 2, 3, 4 or 5, preferably 1, 2 or 3, substituents. Suitable substituents include alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylsulfanyl, halogen, NR ^c R ^d, hydroxyl, cyano, nitro, COOR ^b where R ^b is hydrogen or a metal ion. Examples of substituted aryl include 2-, 3- and 4-methylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl, 2,4-, 2, 5-, 3,5- and 2,6-di-n-propylphenyl, 2,4,6-tri-n-propylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl, 2,4-, 2,5-, 3,5- and 2,6-diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-, 3- and 4-sec-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-sec-butylphenyl, 2,4,6-tri-sec-butylphenyl, 2-, 3 and 4-tert-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-tert-butylphenyl and 2,4,6-tri-tert-butylphenyl; 2-, 3- and 4-methoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-, 3- and 4-ethoxyphenyl, 2 , 4-, 2,5-, 3,5- and 2,6-

Diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-, 3- and 4-propoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropoxyphenyl, 2-, 3- and 4-isopropoxyphenyl , 2,4-, 2,5-, 3,5- and 2,6-diisopropoxyphenyl and 2-, 3- and 4-butoxyphenyl. The term "aryloxy" represents an aryl group as mentioned above which is bonded via the oxygen atom (-O-), for example phenyloxy, 1-napthyloxy or 2-naphthyloxy.

The term "heterocycloalkyl" in the context of the present invention comprises non-aromatic, unsaturated or fully saturated cycloaliphatic groups having in general 4 to 12 ring atoms, preferably 5 to 9 ring atoms, in which 1, 2 or 3 of the ring carbon atoms are selected from hetero atoms selected from the elements Oxygen, nitrogen and sulfur are replaced. Heterocycloalkyl may be unsubstituted or substituted, wherein in the case of a substitution, these heterocyclic groups generally carry 1, 2 or 3, preferably 1 or 2, particularly preferably a substituent. Suitable substituents include alkyl, alkoxy, alkylcarbonyl, carbonyl Alkoxycar-, alkylsulfanyl, halogen, NR ^c R ^d, hydroxyl, cyano, nitro, COOR ^b where R ^b is hydrogen or a metal ion and R ^c and R ^d independently are hydrogen , Cycloalkyl, aryl, heteroaryl or heterocyclyl. Exemplary of heterocycloaliphatic groups are pyrrolidinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, morpholidinyl, thiazolidinyl, isothiazolidinyl, isoxazolidinyl, piperazinyl, tetrahydrothiophenyl, di-hydrothien-2-yl, tetrahydrofuranyl, Dihydrofuran-2-yl, tetrahydropyranyl, 1, 2-oxazolin-5-yl, 1, 3-oxazolin-2-yl and dioxanyl.

The term "heteroaryl" in the context of the present invention comprises a mono-, di- or trinuclear aromatic ring system containing in general 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, which in addition to carbon atoms Examples of heteroaryl include furyl, thiophenyl, pyridinyl, quinolinyl, acridinyl, pyridazinyl, pyrimindinyl, pyrazinyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, purinyl, indazolinyl, etc., embedded image 1, 2, 3, or 4 selected from nitrogen, oxygen, and sulfur , Benzotriazolyl, 1, 2,3-triazolyl, 1, 3,4-triazolyl and carbazolyl These heteroaromatic groups may be unsubstituted or substituted In the case of substitution, heteroaryl generally has 1, 2 or 3 substituents, preferably under alkyl, Alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylsulfanyl, halogen, NR ^c R ^d , hydroxy, cyano, nitro, COOR ^b where R ^{b is} hydrogen or a metal ion equivalent and R ^c and R ^{d are} independent ig of each other are hydrogen, cycloalkyl, aryl, heteroaryl or heterocyclyl, are selected.

Halogen is fluorine, chlorine, bromine or iodine.

The term "halide" stands for the singly negatively charged halogen anions, preferably for F ", Ch, Br and I". The term "pseudohalide" refers to a single negative charge Functional groups that are similar to halides in their properties. Typically these include CN, N ₃ ^", OCN, ^CNO", SCN, NCS, ^"SeCN- and CIO ^_4". Preferably, this invention is CIO ₄ ^" and CN-.

The term "barbituric acid residue" is used for a substituent attached via the "C5 atom" of the 2,4,6-trihydroxypyrimidine skeleton and for the stabilized tautomers of barbituric acid derivatives obtained by single or double N-alkylation.

The term "dimedone" refers to a substituent attached via the "C3 atom" of the 5,5-dimethyl-1,3-cyclohexanedione parent structure.

Y ^1, Y ^2, Y ³ and Y ⁴ are preferably each independently oxygen or NR ^17, and most preferably oxygen.

R ¹⁷ is preferably hydrogen or an unsubstituted C 1 -C ₄ -alkyl, such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, and preferably methyl, ethyl or n-butyl, particularly preferred for methyl or ethyl, and most preferably for methyl.

R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each preferably, independently of one another, C 1 -C 6 -alkyl, C 6 -C 10 -aryl or C 5 -C 12 -cycloalkyl, in particular C 1 -C 6 -alkyl and C 6 -C 10 -aryl, and particularly preferably selected from methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl , Heptadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1-dimethylbutyl, 1, 1, 3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1 (p-butylphenyl) -ethyl, phenyl, toIyI (methylphenyl), xylene (trimethylphenyl), α-naphthyl, β-naphthyl, 4-diphenylyl, dimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl and dodecylphenyl, in particular selected from among methyl, ethyl, propyl, n-butyl, hexyl, octyl, 2-ethylhexyl, dodecyl, benzyl, 2-phenylethyl, phenyl, ToIyI, α-naphthyl and ß-naphthyl and especially selected from the group consisting of meth yl, ethyl, n -propyl, n-butyl, benzyl, phenyl and ToIyI.

According to the invention of the radicals R ¹³ to R ¹⁶ at least one radical is a Ci-Cis-alkyl and at least one further radical is a C6-Ci ₄ -aryl, preferably at least one radical is a Ci-Cis-alkyl, another radical is a C6 -Cio-aryl and the other two radicals are also selected from Ci-Cis-alkyl and C6-Cio-aryl. More preferably, at least one radical is a Ci-Cis-alkyl and at least two further radicals are Cδ-Cio-aryl. Most preferably, one of the radicals is a Ci-Cis-alkyl and the other three radicals are C6-Cio-aryl.

The preparation of the cyanine dyes used in the stabilizer compositions according to the invention can be carried out by various methods. They can be prepared, for example, by means of a two-stage process in which, in a first step, the cyanine cations are synthesized with customary anions such as iodide, tetrafluoroborate, perchlorate or paratoluenesulfonate. Production instructions are known to the person skilled in the art. As an example, reference is made to DE 3721850, EP 627 660 and the literature cited therein. Some salts of cyanine cations are also commercially available.

In a second step, if appropriate, the customary anions are then exchanged for the anions An ^m "according to the invention by means of a suitable process.

This can be done, for example, by introducing the starting material together with the corresponding acid H _m An in a water-immiscible organic solvent or solvent mixture, wherein the resulting stabilizer (A) need not be soluble therein. Particularly suitable are volatile organic solvents with a certain polarity. For example, it may be haloalkanes, such as. For example, dichloromethane. The organic solution or suspension is then extracted with water until the original anion is completely removed from the organic solution. The cyanine dye used according to the invention can subsequently be isolated by removal of the solvent.

The preparation can also be carried out using acidic ion exchange resins.

Alternatively, the ion exchange can be carried out in analogy to the method disclosed in WO 0376518.

According to the invention, the stabilizer compositions used also contain a component (B) of an anionic boron compound of the formula (VII).

These anionic boron compounds have as counterion an x-fold positively charged cation Kat ^{x +} . These may be, for example, (alkaline earth) or ammo- For example, Mg ²⁺ , Li ⁺ , Na ⁺ or K ⁺ , however, are preferably ammonium ions.

For the purposes of the present invention, ammonium ions are ionic compounds which contain at least one tetra-substituted nitrogen atom, the substituents being selected from C 1 -C 6 -alkyl and C 6 -C 14 -aryl, alkyl-substituted ammonium ions are preferably used. Of course, two or more substituents may also be linked to form a ring, so that the quaternary nitrogen atom is part of a five- to seven-membered ring. Examples of ammonium cations are tetra-n-octylammonium, tetramethylammonium, tetraethylammonium, tetra-n-butylammonium, trimethylbenzylammonium, trimethylcetylammonium, triethylbenzylammonium, tri-n-butylbenzylammonium, trimethylethylammonium, tri-n-butylethylammonium, triethylmethylammonium, tri-n-butyl butylmethylammonium, di- isopropyl-diethylammonium, di-isopropyl-ethyl-methyl ammonium, di-isopropyl-ethyl-benzylammonium, N, N-dimethyl, N, N-dimethylmorpholinium, N ₁ N- dimethylpiperazinium or N-methyl-diazabicyclo [2.2. 2] octane.

Preferred alkylammonium ions are tetraoctylammonium, tetramethylammonium, tetraethylammonium and tetra-n-butylammonium, particular preference is given to tetraethylammonium and tetra-n-butylammonium, and very particular preference is given to tetra-n-butylammonium.

Ammonium ions containing ring systems are, for example, methylated, ethylated, n-butylated, cetylated or benzylated piperazines, piperidines, imidazoles, morpholines, quinuclidines, quinolines, pyridines or triethylenediamines.

The stabilizer compositions according to the invention contain at least one component (A) of the formula V _m An ^{m "} Cya ⁺ , as stated above, and at least one component (B), preferably this is described by formula (VII) and has a counterion V _x Kat ^{x +} .

The stabilizer compositions according to the invention may contain, as component (B), instead of or in addition to the anionic boron compounds of the formula (VII) and their counterion V _x Kat ^{x +,} also sulfonium salts, iodonium salts, sulfones, peroxides, pyridine N-oxides or halomethyltriazines ,

Suitable sulfonium salts are described, for example, on page 3, lines 28-39 DE 19730498, which is hereby expressly the subject of the present disclosure by reference. These are preferably those of the formula

R ¹⁸

■ + AnA-

R ²⁰ ^ R ¹⁹

wherein

R ¹⁸ and R ^{19 are} each an optionally substituted aryl group, and R ^{20 is} an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted cycloalkyl group or an optionally substituted aryl group, and AnA- is an anion equivalent.

Particularly preferred are triphenylsulfonium, diphenylanisylsulfonium, diphenyl (4-tolyl) sulfonium, diphenyl (4-fluorophenyl) sulfonium, diphenyl [4- (phenylthio) phenyl] sulfonium, diphenylbenzylsulfonium, diphenyl (4-chlorobenzyl) -sulfonium, diphenyl- (4-bromobenzyl) sulfonium, diphenyl- (4-cyano-benzyl) -sulfonium, di (4-tert-butylphenyl) -benzylsulfonium, dianisyl (4-bromobenzene) sulfonium, diphenylphenacylsulfonium, diphenyl- (4-chlorophenacyl ) sulfonium, diphenyl- (4-cyanophenacyl) -sulfonium, diphenylallyl-sulfonium, diphenylmesylsulfonium, diphenyl-p-toluenesulfonylmethylsulfonium, diphenyl- (dimethylsulfoniummethyl) -sulfonium and diphenyl-4- (diphenylsulfonium) -phenyl] -sulfonium.

Preferred anion equivalents AnA- are BF ₄ -, PFβ ^" , AsFβ ^" , SbFβ ^" , CIO ₄ ^" , Ch, Br, tetraphenylborate, tetrakis (pentafluorophenyl) borate, the benzenesulfonate anion, the p-toluenesulfonate anion and the trifluoromethanesulfonate anion.

Suitable iodonium salts are described, for example, on page 3, lines 40-43 of DE 19730498, which is hereby expressly the subject of the present disclosure by reference.

These are preferably iodonium salts of the formula

wherein R ²¹ and R ^{22 are} optionally substituted aryl groups and AnB- is an anion. Particularly preferred are diphenyliodonium, anisylphenyliodonium, di (4-tert-butylphenyl) iodonium, di (4-chlorophenyl) iodonium, di-tolyliodonium and di (3-nitrophenyl) iodonium.

Preferred anions AnB- are BF ₄ ^" , PFβ ^" , AsFβ ^" , SbFβ ^" , CIO ₄ ^" , Cl ^" , Br, tetraphenylborate, tetrakis (pentafluorophenyl) borate, the benzenesulfonate anion, the p-toluenesulfonate anion and the trifluoromethanesulfonate anion.

Suitable sulfones are described, for example, on page 4, lines 1-12 of DE 19730498, which is hereby expressly the subject of the present disclosure by reference.

These are preferably those of the formula

wherein

R ^{23 is} an optionally substituted aryl group and the radicals R ^{24 are} each a halogen atom.

Halogen in the context of this document comprises fluorine, chlorine, bromine and iodine, preferably chlorine and bromine and particularly preferably chlorine.

Particular preference is given to trichloromethylphenylsulfone, tribromomethylphenylsulfone, trichloromethyl-4-chlorophenylsulfone, tribromomethyl-4-nitrophenylsulfone,

Trichloromethylbenzothiazolesulfone, 2,4-dichlorophenyltrichloromethylsulfone, 2-methyl-4-chlorophenyltrichloromethylsulfone and 2,4-dichlorophenyltribromomethylsulfone.

Suitable peroxides are described, for example, on page 4, lines 13-24 of DE 19730 498, which is hereby expressly the subject of the present disclosure by reference.

These are preferably those of the formula

wherein

R ^{25 is} an optionally substituted aryl group and

R ^{26 represents} an optionally substituted alkyl group, an optionally substituted aryl group or an optionally substituted benzoyl group, preferably of the formula R ²⁵ - (CO) -.

Particular preference is given to benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, di- (tert-butylperoxy) isophthalate, di- (tert-butylperoxy) terephthalate, di (tert-butylperoxy) phthalate, 2.5- Dimethyl di- (benzoylperoxy) -hexane and 3,3 ', 4,4'-tetra- (tert-butylperoxycarbonyl) -benzophenone.

Suitable pyridine N-oxides are described, for example, on page 3, lines 44-62 of DE19730498, which is hereby expressly the subject of the present disclosure by reference.

These are preferably those of the formula

wherein

R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ or R ³¹ each independently represents a hydrogen atom, a halogen atom, a cyano group, an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted aryl group, R ^{32 represents} an optionally substituted alkyl group and AnC "stands for an anion equivalent.

Particularly preferred are N-methoxypyridinium, N-ethoxypyridinium, N-methoxy-2-picolinium, N-methoxy-3-picolinium, N-ethoxy-2-picolinium, N-ethoxy-3-picolinium, N-methoxy-4-bromopyridinium , N-methoxy-3-bromopyridinium, N-methoxy-2-bromopyridinium, N-ethoxy-4-bromopyridinium, N-ethoxy-3-bromopyridinium, N-ethoxy-2-bromopyridinium, N-ethoxy-4-chloropyridinium, N Ethoxy-3-chloropyridinium, N-ethoxy-2-chloropyridinium, N-methoxy-4-methoxypyridinium, N-methoxy-3-methoxypyridinium, N-methoxy-2-methoxypyridinium, N-ethoxy-4-methoxypyridinium, N-ethoxy -3- methoxypyridinium, N-ethoxy-2-methoxypyridinum, N-methoxy-4-phenylpyridinium, N-methoxy-3-phenylpyridinium, N-methoxy-2-phenylpyridinium, N-ethoxy-4-phenylpyridinium, N-ethoxy-3-phenyl- pyridinium, N-ethoxy-2-phenylpyridinium, N-methoxy-4-cyanopyridinium, N-ethoxy-4-cyanopyridinium, N, N'-dimethoxy-4,4'-bipyridinium, N, N'-diethoxy-4,4 '-bipyridinium, N, N'-dimethoxy-2,2'-bipyridinium and N, N'-diethoxy-2,2'-bipyridinium.

Preferred anions AnC ^" are BF ₄ ^" , PFβ ^" , AsFβ ^" , SbFβ ^" , CIO ₄ ^" , Cl ^" , Br, tetraphenylborate, tetrakis (pentafluorophenyl) borate, the benzenesulfonate anion, the p-toluenesulfonate anion and the trifluoromethanesulfonate anion.

Suitable halomethyltriazines are described, for example, on page 4, lines 25-40 of DE 19730498, which is hereby expressly the subject of the present disclosure by reference.

These are preferably compounds which are described by the following formula

R ³³

N ^' ~ N

R ³⁵ ^ NO

wherein

R ³³ , R ³⁴ and R ³⁵ each independently represent a trihalomethyl group, an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted aryl group, with the proviso that at least one of the groups is a trihalomethyl group.

Particularly preferred are 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) s-triazine, 2,4-bis (dichloromethyl) -6-trichloromethyl-s-triazine , 2-propionyl-4,6-bis- (trichloromethyl) -s-triazine, 2-benzoyl-4,6-bis- (trichloromethyl) -s-triazine, 2- (4-

Cyanophenyl 4,6-bis (trichloromethyl) -s-triazine, 2- (4-nitrophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-chlorophenyl-4,6-bis - (trichloromethyl) -s-triazine, 2- (4-cumenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-aminophenyl) -4,6-bis (trichloromethyl) -s triazine, 2,4-bis (4-methoxyphenyl) -6-trichloromethyl, 2,4-bis (3-chlorophenyl) -6-trichloromethyl-s-triazine, 2- (4-methoxystyryl- (trichloromethyl) - s-triazine, 2- (4-chlorostyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-aminophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2, 4-bis (4-methoxyphenyl) - 6-trichloromethyl-s-triazine, 2,4-bis (3-chlorophenyl) -6-trichloromethyl-s-triazine, 2- (4-methoxystyryl) -4,6-bis- (trichloromethyl) -s-triazine, 2- (4-chlorostyryl) -4,6-bis- (trichloromethyl) -s-triazine, 2- (4-aminostyryl) -4,6-bis (dichloromethyl) -s-triazine, 2- (4'- Methoxy-1'-naphthyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (6'-nitro-1'-naphthyl) -4,6-bis (trichloromethyl) -s-triazine.

Another object of the invention relates to the use of one of the above-defined stabilizer compositions, which contains as additional component (C) a transition metal complex or a salt of a transition metal.

Component (C) is preferably selected from main group and transition metal complexes or salts thereof, preferably transition metal complexes or transition metal salts, in particular from transition metals of groups 7 to 11 of the Periodic Table of the Elements. Suitable metals and their oxidation state include, but are not limited to, manganese II or IM, iron II or IM, cobalt II or IM, nickel II or IM, copper I or M, rhodium M, IM or IV, and ruthenium. The oxidation states of the added metals do not necessarily have to correspond to the active form. The metal is preferably selected from iron, nickel, manganese, cobalt or copper, more preferably under manganese or cobalt and in particular the metal is cobalt. Suitable counterions are, for example, chloride, acetate, stearate, palmitate, 2-ethylhexanoate, neodecanoate or naphthylate.

If component C) is present, it is preferably used in an amount of 0.001% by weight to 1% by weight, based on the total weight of the packaging material, in particular in an amount of 0.001% by weight to 0.1 wt .-%.

Another object of the invention relates to the use of one of the above-defined stabilizer compositions, which contains as additional component (D) at least one ethylenically unsaturated compound.

Component (D) is preferably selected from olefinically unsaturated compounds which are customarily used as binders, reactive diluents, radiation-curable polymers or antioxidants. Suitable components (D) are, for example, esters of (meth) acrylic acid with alcohols having 1 to 20 carbon atoms, for example methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl ester, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, dihydrodicyclopentadienyl acrylate, vinylaromatic compounds, for example styrene, divinylbenzene, α, β-unsaturated nitriles, for example acrylonitrile, methacrylonitrile, α, β-unsaturated aldehydes, for example acrolein, methacrolein, vinyl esters, for example vinyl acetate , Vinyl propionate, halogenated ethylenically unsaturated compounds, for example vinyl chloride, vinylidene chloride, conjugated unsaturated compounds, for example butadiene, isoprene, chloroprene, monounsaturated compounds, for example ethylene, propylene, 1-butene, 2-butene, isobutene, cyclic monounsaturated compounds, for example cyclopentene, Cyclohexene, cyclododecene, N-vinylformamide, allylacetic acid, vinylacetic acid, monoethylenically unsaturated carboxylic acids having 3 to 8 carbon atoms and their water-soluble alkali metal, alkaline earth metal or ammonium salts such as, for example, acrylic acid, methacrylic acid, dimethylacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylenemalonic acid , Crotonic acid, fumaric acid, mesaconic acid and itaconic acid, N-vinylpyrrolidone, N-vinyllactams, such as N-vinylcaprolactam, N-vinyl-N-alkylcarboxamides or N-vinylcarboxamides, such as N-vinylacetamide, N-vinyl N-methylformamide and N-vinyl-N-methylacetamide or vinyl ethers, for example methyl vinyl ether, ethyl vinyl ether, n-prop yl vinyl ethers, isopropyl vinyl ethers, n-butyl vinyl ethers, sec-butyl vinyl ethers, isobutyl vinyl ethers, tert-butyl vinyl ethers, 4-hydroxybutyl vinyl ethers, (meth) acrylate compounds such as polyester (meth) acrylates, polyether (meth) acrylates, urethane (meth) acrylates, epoxides xy (meth) acrylates, carbonate (meth) acrylates, silicone (meth) acrylates, acrylated polyacrylates, carotenoids, carotenes (e.g. B. α-carotene, ß-carotene, lycopene) and their derivatives, chlo- roergic acids and their derivatives, vitamin C and derivatives (eg ascorbyl palmitate, Mg ascorbyl phosphate, ascorbol acetate), tocopherols and derivatives (eg -E acetate), vitamin A and derivatives (Vita min-A-pa Imitat), as well as mixtures of two or more than two of the aforementioned compounds.

In this application, (meth) acrylic acid is methacrylic acid and acrylic acid, preferably acrylic acid.

Another object of the invention relates to methods for the protection of packaged products from light, heat and / or oxygen, in which one uses for the preparation of the packaging a plastic containing at least one of the above-mentioned stabilizer compositions.

Plastics in which the stabilizer composition can be used usually contain at least one polymer component selected from polyolefins, polyolefin copolymers, polytetrafluoroethylenes, ethylene-tetrafluoroethylene copolymers, polyvinyl chlorides, polyvinylidene chlorides, polyvinyl alcohols, polyvinyl esters, polyvinylalkanals, polyvinyl ketals, Polyamides, polyimides, polycarbonates, polycarbonate blends, polyesters, polyester blends, poly (meth) acrylates, poly (meth) acrylate-styrene copolymer blends, poly (meth) acrylate-polyvinylidene difluoride blends, polyurethanes, polystyrenes, Styrene copolymers, polyethers, polyether ketones, polysulfones and mixtures thereof. Another object of the present invention relates to the use of a stabilizer composition in a packaging material which contains at least one polymer or at least consists of a polymer.

In particular, this polymer is selected from polyolefins, polyolefin copolymers, polytetrafluoroethylenes, ethylene-tetrafluoroethylene copolymers, polyvinyl chlorides, polyvinylidene chlorides, polyvinyl alcohols, polyvinyl esters, polyvinylalkanals, polyvinyl ketals, polyamides, polyimides, polycarbonates, polycarbonate blends, polyesters, polyester blends, Poly (meth) acrylates, poly (meth) acrylate-styrene copolymer blends, poly (meth) acrylate-polyvinylidene difluoride blends, polyurethanes, polystyrenes, styrenic copolymers, polyethers, polyether ketones, polysulfones, and mixtures thereof.

Preference is given here to polymers from the group of polyolefins, polyolefin copolymers, polyvinylalkanals, polyamides, polycarbonates, polycarbonate-polyester blends, polycarbonate-styrene copolymer blends, polyesters, polyester blends, poly (meth) acrylates, poly (meth) acrylate-styrene copolymer blends, poly (meth) acrylate-polyvinylidene difluoride blends, styrenic copolymers and polysulfones, and mixtures thereof.

Particularly preferred polymers are transparent or at least translucent. Examples include: polyethylene, polypropylene, polyvinyl butyral, polyamide [6], polyamide [6,6], polycarbonate, polycarbonate-polyethylene terephthalate blends, polycarbonate-polybutylene terephthalate blends, polycarbonate-acrylonitrile / styrene / acrylonitrile copolymer blends , Polycarbonate-acrylonitrile-butadiene-styrene copolymer blends, methyl methacrylate-acrylonitrile-butadiene-styrene polymer (MABS), polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, impact-modified polymethyl methacrylate, polybutyl acrylate, polymethyl methacrylate-polyvinylidene difluoride blends, acrylonitrile / buta - diene / styrene copolymers (ABS), styrene / acrylonitrile copolymers (SAN), acrylonitrile / styrene / acrylic ester polymer (ASA) and polyphenylene sulfone and mixtures thereof.

Suitable and preferred polymer components are specified in more detail below:

A preferred embodiment of the present invention relates to a packaging material wherein the polymer is selected from polyolefins, polyolefin copolymers and polymer blends containing at least one polyolefin homo- or copolymer. For example, polymers which are composed of olefins without further functionality, such as polyethylene, polypropylene, polybutene-1 or polyisobutylene, poly-4-methylpent-1-ene, polyisoprene, polybutadiene, polymers of cycloolefins, for example cyclopentene or norbornene and copolymers of Mono- or diolefins such as polyvinylcyclohexane.

Ethylene polymers:

Suitable polyethylene (PE) homopolymers whose classification is based on the density are, for example:

Ultra-low density (ULD) UL, very low density VLD (VLD); Co- and terpolymers of ethylene with up to 10% octene, 4-methylpentene-1 and sometimes propylene; Density between 0.91 and 0.88 g / cm ³ ; hardly crystalline, transparent

PE-LD (LD = low density), available for. B by the high pressure process (ICI) at 1000 to 3000 bar and 150 to 300 ° C with oxygen or peroxides as catalysts in autoclaves or tubular reactors. Highly branched with differently long branches, crystallinity 40 to 50%, density 0.915 to 0.935 g / cm ³ , average molecular weight up to 600 000 g / mol.

LLDPE (LLD = linear low density), obtainable with metal complex catalysts in the low pressure process from the gas phase, from a solution (eg gasoline), in a suspension or with a modified high pressure process. Weak branches with intrinsically unbranched side chains, molecular weights higher than PE-LD.

PE-MD (MD = middle-density); the density is between 0.93 and 0.94 g / cm ³ ; can be prepared by mixing PE-LD and PE-HD or directly as a copolymer LLDPE.

PE-HD (HD = High Density), available according to the medium pressure (Phillips) and low pressure (Ziegler) method. According to Phillips at 30 to 40 bar, 85 to 180 ° C, chromium oxide as a catalyst, molecular weights about 50 000 g / mol. After Ziegler at 1 to 50 bar, 20 to 150 ° C, titanium halides, titanium esters or aluminum alkyls as catalysts, molecular weight about 200 000 to 400 000 g / mol. Execution in suspension, solution, gas phase or mass. Very weakly branched, crystallinity 60 to 80%, density 0.942 to 0.965 g / cm ³ . PE-HD-HMW (HMW = high molecular weight), obtainable by Ziegler, Phillips or gas phase method. High density and high molecular weight.

Ultra high molecular weight (UHMW) UHMW available with modified Ziegler catalyst, molecular weight 3,000,000 to 6,000,000 g / mol.

Particularly suitable is polyethylene produced in a gas phase fluidized bed process using catalysts (usually supported), e.g. Lupolene® (Basell, The Netherlands).

Especially preferred is polyethylene produced using metallocene catalysts. Such polyethylene is e.g. available as Luflexen® (Basell, The Netherlands).

The ethylene copolymers are usually random copolymers or block or impact copolymers. Suitable block or impact copolymers of ethylene and comonomers are, for. B. polymers in which in the first stage, a homopolymer of the comonomer or a random copolymer of the comonomer, for example, with up to 15 wt .-% ethylene produces and then in the second stage, a comonomer-ethylene copolymer having ethylene contents of 15 to 80% by weight polymerized. In general, as much of the comonomer-ethylene copolymer is copolymerized to the extent that the copolymer produced in the second stage has a content of from 3 to 60% by weight in the end product.

The polymerization for the preparation of the ethylene-comonomer copolymers can be carried out by means of a Ziegler-Natta catalyst system. However, it is also possible to use catalyst systems based on metallocene compounds or on the basis of polymerization-active metal complexes.

The field of application of LD-PE extends from films over paper coating to thick and thin-walled moldings, for example bottles. LLD-PE shows advantages over LDPE in mechanical properties and in stress cracking resistance. Application of LLDPE is mainly found in films.

Propylene polymers:

The term polypropylene is to be understood below as meaning both homopolymers and copolymers of propylene. Copolymers of propylene contain minor amounts of monomers copolymerizable with propylene, for example C2- Cβ-Alk-1-enes such as ethylene, but-1-ene, pent-1-ene or hex-1-ene. Two or more different comonomers can also be used.

Suitable polypropylenes are i.a. Homopolymers of propylene or copolymers of propylene with up to 50 wt .-% of copolymerized other alk-1-enes having up to 8 carbon atoms. The copolymers of propylene are random copolymers or block or impact copolymers. If the copolymers of propylene have a random structure, they generally contain up to 15% by weight, preferably up to 6% by weight, of other alk-1-enes having up to 8 carbon atoms, in particular ethylene, but-1 -en or a mixture of ethylene and but-1-ene.

Suitable block or impact copolymers of propylene are, for. B. Polymers in which in the first stage, a propylene homopolymer or a random copolymer of propylene with up to 15 wt .-%, preferably up to 6 wt .-%, of other alk-1-ene with up to 8 C And then in the second stage a propylene

Ethylene copolymer having ethylene contents of 15 to 80 wt .-%, wherein the propylene-ethylene copolymer may additionally contain further C ₄ -Cs-AIk-I -ene addition, lymerisiert. As a rule, so much of the propylene-ethylene copolymer is added to it that the copolymer produced in the second stage has a content of from 3 to 60% by weight in the end product.

The polymerization for the production of polypropylene can be carried out by means of a Ziegler-Natta catalyst system. Particular preference is given to using those catalyst systems which, in addition to a titanium-containing solid component a), also comprise cocatalysts in the form of organic aluminum compounds b) and electron donor compounds c).

However, it is also possible to use catalyst systems based on metallocene compounds or on the basis of polymerization-active metal complexes.

The preparation of the polypropylenes is usually carried out by polymerization in at least one, often in two or more successive reaction zones (reactor cascade), in the gas phase, in a suspension or in a liquid phase (bulk phase). The usual reactors used for the polymerization of C 2 -C 5 -alk-1-enes can be used. Suitable reactors include continuously operated stirred tanks, loop reactors, powder bed reactors or fluidized bed reactors. The polymerization for the preparation of the polypropylene used is carried out under conventional reaction conditions at temperatures of 40 to 120 ° C, in particular from 50 to 100 ° C and pressures of 10 to 100 bar, in particular from 20 to 50 bar.

Suitable polypropylenes generally have a melt flow rate (MFR), according to ISO 1 133, of 0.1 to 200 g / 10 min., In particular from 0.2 to 100 g / 10 min., At 230 ° C and under a weight of 2.16 kg, up.

In a further embodiment of the invention, the plastic contains at least one polyolefin. Preferred polyolefins contain at least one copolymerized monomer selected from among ethylene, propylene, but-1-ene, isobutylene, 4-methyl-1-pentene, butadiene, isoprene and mixtures thereof. Homopolymers, copolymers of the stated olefin monomers and copolymers of at least one of the stated olefins as the main monomer and other monomers (such as, for example, vinylaromatics) as comonomers are suitable.

Preferred polyolefins are low density polyethylene homopolymers (PE-LD), the ethylene-vinyl acetate copolymer (E / VA) and polypropylene homopolymers and polypropylene copolymers. Preferred polypropylenes are, for example, biaxially oriented polypropylene (BOPP) and crystallized polypropylene. Preferred blends of the aforementioned polyolefins are, for example, blends of polypropylene with polyisobutylene, polypropylene with polyethylene (e.g., PP / HDPE, PP / LDPE), and blends of various types of polyethylene (e.g., LDPE / HDPE).

Another preferred embodiment of the present invention relates to a packaging material containing as polymer a halogen-containing polymer. Halide-containing polymers include polytetrafluoroethylene homo and copolymers, polychloroprene, chlorinated and fluorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halo-rubber), chlorinated and sulfochlorinated polyethylene, copolymers of ethylene and chlorinated Ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, in particular polymers of halogen-containing vinyl compounds, for. As polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyvinyl fluoride, polyvinylidene fluoride and copolymers thereof, such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers. Polyvinyl chloride is used with different content of plasticizers, with a content of plasticizers of 0 - 12% as rigid PVC, of more than 12% as soft PVC or with a very high content of plasticizers as PVC paste. Typical plasticizers are, for example, phthalates, epoxides, adipic acid esters. Polyvinyl chloride is prepared by radical polymerization of vinyl chloride in bulk, suspension, microsuspension and emulsion polymerization. The polymerization is often initiated by peroxides.

Polyvinylidene chloride is prepared by radical polymerization of vinylidene chloride. Vinylidene chloride can also be copolymerized with (meth) acrylates, vinyl chloride or acrylonitrile. Polyvinylidene chloride and the vinylidene copolymers are processed into films, for example, but also into profiles, tubes and fibers. One important application relates to multilayer films; the good barrier properties of the polyvinylidene chloride are also used for coatings.

A further preferred embodiment of the present invention relates to a packaging material, wherein the polymer is selected from homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, for. For example, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers. Polyalkylene glycols are formed by polyaddition of a cyclic ether such as ethylene oxide, propylene oxide or tetrahydrofuran with an OH compound as a starter molecule, such as water. Starter molecules for the polyaddition may also be dihydric or polyhydric alcohols.

A further preferred embodiment of the present invention relates to a packaging material, wherein the polymer is selected from polyacetals, copolymers of polyacetals with cyclic ethers and polyacetals, which are modified with thermoplastic polyurethanes, acrylates or methyl acrylate / butadiene / styrene copolymers. Polyacetals are formed by polymerization of aldehydes or cyclic acetals. A technically important polyacetal is polyoxymethylene (POM), which is obtainable by cationic or anionic polymerization of formaldehyde or trioxane. Modified POM is obtained for example by copolymerization with cyclic ethers such as ethylene oxide or 1, 3-dioxolane. The combination of POM with thermoplastic polyurethane elastomers gives POM-based polymer blends. Unreinforced POM is characterized by very high stiffness, strength and toughness.

A further preferred embodiment of the present invention relates to a packaging material, wherein the polymer is selected from polyarylethers, polyarylsulphides and mixtures of polyarylethers with styrene polymers and polyamides. An example of polyaryl ethers are polyphenylene oxides whose main chain consists of phenylene units linked via oxygen atoms, which are optionally substituted by alkyl groups are substituted, is constructed. A technically significant polyphenylene oxide is poly-2,6-dimethylphenyl ether. An example of polyaryl sulfides are polyphenylene sulfides obtainable by polycondensation of 1, 4-dichlorobenzene with sodium sulfide.

Another preferred embodiment of the present invention relates to a packaging material wherein the polymer is selected from polyurethanes. Suitable polyisocyanate polyaddition products (polyurethanes) are, for example, cellular polyurethanes, e.g. rigid or soft polyurethane foams, compact polyurethanes, thermoplastic polyurethanes (TPU), thermosetting or elastic polyurethanes or polyisocyanurates. These are well known and their preparation is described many times. It is usually carried out by reacting dihydric and higher isocyanates or corresponding isocyanate analogues with isocyanate-reactive compounds. The preparation is carried out by customary processes, for example by the one-shot process or by the prepolymer process, e.g. in molds, in a reaction extruder or even a belt system. A special manufacturing process is the Reaction Injection Molding (RIM) process, which is preferably used to produce polyurethanes having a foamed or compact core and a predominantly compact, non-porous surface. The polymer compositions used according to the invention are advantageously suitable for all these processes.

Polyurethanes are generally composed of at least one polyisocyanate and at least one compound having at least two isocyanate-reactive groups per molecule. Suitable polyisocyanates preferably have 2 to 5 NCO groups. The isocyanate-reactive groups are preferably selected from hydroxyl, mercapto, primary and secondary amino groups. These preferably include di- or higher polyols.

Suitable polyisocyanates are aliphatic, cycloaliphatic, araliphatic and aromatic isocyanates. Suitable aromatic diisocyanates are, for example, 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 1, 5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-tolylene diisocyanate (TDI), diphenylmethane diisocyanate, 3,3'-dimethyl-diphenyl diisocyanate, 1, 2-diphenylethane diisocyanate and / or Phenylendiisocy- anat. Aliphatic and cycloaliphatic diisocyanates include, for example, tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, 2-ethylbutylene-1,4-diisocyanate, 1 -isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 1, 4- and / or 1, 3-bis (isocyanatomethyl) cyclohexane (HXDI), cyclohexane-1, 4- diisocyanate, 1-methyl-2,4- and / or 2,6-cyclohexanediisocyanato and / or 4,4'-, 2,4'- and / or 2,2'-dicyclohexyl- diisocyanate methane. Preferred diisocyanates include hexamethylene diisocyanate (HMDI) and isophorone diisocyanate. Examples of higher functionality isocyanates are triisocyanates, e.g. B. Triphenylmethane-4,4 ', 4 "-triisocyant, furthermore the cyanurates of the aforementioned diisocyanates, as well as the oligomers obtainable by partial reaction of diisocyanates with water, for example the biurets of the aforementioned diisocyanates, furthermore oligomers obtained by targeted reaction of semiblocked diisocyanates with polyols having on average more than 2 and preferably 3 or more hydroxy groups.

High-functional polyols, especially polyether polyols based on highly functional alcohols, sugar alcohols and / or saccharides, are used as starter molecules for polyolefin rigid foams, which may optionally have isocyanurate structures. For flexible polyisocyanate polyaddition products, e.g. Flexible polyurethane foams or RIM materials, are 2- and / or 3-functional polyether polyols based on glycerol and / or trimethylolpropane and / or glycols as starter molecules as polyols and 2- and / or 3-functional polyether-based polyols based on glycerol and / or or trimethylolpropane and / or glycols as alcohols to be esterified as polyols. Thermoplastic polyurethanes are usually based on predominantly difunctional polyester polyalcohols and / or polyether polyalcohols, which preferably have an average functionality of from 1.8 to 2.5, particularly preferably from 1.9 to 2.1.

The preparation of the polyether polyols is carried out according to a known technology. Suitable alkylene oxides for preparing the polyols are, for example, 1,3-propylene oxide, 1,2- or 2,3-butylene oxide, styrene oxide and preferably ethylene oxide and 1,2-propylene oxide. The alkylene oxides can be used individually, alternately in succession or as mixtures. Preferably, alkylene oxides are used which lead to primary hydroxyl groups in the polyol. Particularly preferred polyols used are those which have been alkoxylated with ethylene oxide to complete the alkoxylation and thus have primary hydroxyl groups. Further suitable polyethers are polytetrahydrofurans and polyoxymethylenes. The polyether polyols have a functionality of preferably 2 to 6 and in particular 2 to 4 and molecular weights of 200 to 10,000, preferably 200 to 8,000.

Suitable polyester polyols may be prepared, for example, from organic dicarboxylic acids having 2 to 12 carbon atoms, preferably aliphatic dicarboxylic acids having 4 to 6 carbon atoms, and polyhydric alcohols, preferably diols having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms. The polyester polyols preferably have a functionality of 2 to 4, in particular 2 to 3, and a molecular weight of 480 to 3000, preferably 600 to 2000 and in particular 600 to 1500.

Furthermore, the polyol component may also include diols or higher alcohols. Suitable diols are glycols preferably having 2 to 25 carbon atoms. These include 1, 2-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 10-decanediol, diethylene glycol, 2,2, 4-trimethylpentanediol-1, 5, 2,2-dimethylpropanediol 1, 3, 1, 4-dimethylolcyclohexane, 1, 6-dimethylolcyclohexane, 2,2-bis (4-hydroxyphenyl) -propane (bisphenol A), 2,2 Bis (4-hydroxyphenyl) butane (bisphenol B) or 1, 1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol C). Suitable higher alcohols are for. As trivalent (triols), tetravalent (tetrols) and / or pentavalent alcohols (pentoles). They usually have 3 to 25, preferably 3 to 18 carbon atoms. These include glycerol, trimethylolethane, trimethylolpropane, erythritol, pentaerythritol, sorbitol and their alkoxylates.

To modify the mechanical properties, e.g. However, the hardness, the addition of chain extenders, crosslinking agents, Abstoppern or possibly mixtures thereof may prove advantageous. The chain extenders and / or crosslinkers have, for example, a molecular weight of 40 to 300. For example, aliphatic, cycloaliphatic and / or araliphatic diols having from 2 to 14, preferably from 2 to 10, carbon atoms, e.g. Ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 10-decanediol, 1, 2, 1, 3, 1, 4-dihydroxycyclohexane, diethylene glycol, dipropylene glycol and preferably ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol and bis (2-hydroxyethyl) hydroquinone, triols such as 1, 2,4-, 1, 3,5-trihydroxycyclohexane, glycerol, trimethylolpropane, triethanolamine and low molecular weight hydroxyl-containing polyalkylene oxides based on ethylene and / or 1, 2-propylene oxide and the aforementioned diols and / or triols as starter molecules. Suitable stoppers include, for example, monofunctional alcohols or secondary amines.

A further preferred embodiment of the present invention relates to a packaging material, wherein the polymer is selected from polyureas, polyimides, polyamideimides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles. Polyureas are known to be formed by polyaddition of diamines and diisocyanates. Polyimides whose essential structural element is the mid group in the main chain are formed by reaction of aromatic tetracarboxylic dianhydrides with aliphatic or aromatic diamines. Polyimides are used, inter alia, as adhesives in composites, and also for coatings, thin films, for example as insulating material in microelectronics High modulus fibers used for semi-permeable membranes and as liquid-crystalline polymers.

Another preferred embodiment of the present invention relates to a packaging material wherein the polymer is selected from polyesters, preferably at least one linear polyester. Suitable polyesters and copolyesters are described in EP 0678376, EP 0595413 and US 6 096 854, to which reference is hereby made. Polyesters are known to be condensation products of one or more polyols and one or more polycarboxylic acids. In linear polyesters, the polyol is a diol and the polycarboxylic acid is a dicarboxylic acid. The diol component may be selected from ethylene glycol, 1,4-cyclohexanedimethanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1, 2-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol and 1, 3-cyclohexanedimethanol be selected. Also suitable are diols whose alkylene chain is interrupted one or more times by non-adjacent oxygen atoms. These include diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and the like. In general, the diol contains 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms. Cycloaliphatic diols can be used in the form of their cis or trans isomeric or as a mixture of isomers. The acid component may be an aliphatic, alicyclic or aromatic dicarboxylic acid. The acid component of linear polyesters is generally selected from terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid and Mixtures thereof. Of course, it is also possible to use the functional derivatives of the acid component such as esters, for example the methyl ester, anhydrides or halides, preferably chlorides. Preferred polyesters are polyalkylene terephthalates, and polyalkylene naphthalates, which are obtainable by condensation of terephthalic acid or naphthalenedicarboxylic acid with an aliphatic diol.

Preferred polyalkylene terephthalates are polyethylene terephthalates (PET) which are obtained by condensation of terephthalic acid with diethylene glycol. PET is also available by transesterification of dimethyl terephthalate with ethylene glycol with elimination of methanol to bis (2-hydroxyethyl) terephthalate and its polycondensation to release ethylene glycol. Further preferred polyesters are polybutylene terephthalates (PBT) obtainable by condensation of terephthalic acid with 1,4-butanediol, polyalkylene naphthalates (PAN) such as polyethylene-2,6-naphthalate (PEN), poly-1,4-cyclohexanedimethylene terephthalate (PCT ), as well as copolyesters of polyethylene terephthalate with cyclohexanedimethanol (PDCT), copolyesters of Polybutylene terephthalate with cyclohexanedimethanol. Likewise preferred are copolymers and transesterification products and physical mixtures (blends) of the abovementioned polyalkylene terephthalates. Particularly suitable polymers are selected from poly- or copolycondensates of terephthalic acid, such as polyethylene or copolyethylene terephthalate (PET or CoPET or PETG), poly (ethylene 2,6-naphthalate) s (PEN) or PEN / PET copolymers and PEN / PET blends. The said copolymers and blends may also contain portions of transesterification products, depending on their method of preparation.

PET and PBT have high resistance as thermoplastic materials. PET is widely used as a material for beverage bottles.

Another preferred embodiment of the present invention relates to a packaging material wherein the polymer is selected from polycarbonates, polyester-carbonates and mixtures thereof. Polycarbonates are formed z. B. by condensation of phosgene or carbonic acid esters such as diphenyl carbonate or dimethyl carbonate with dihydroxy compounds. Suitable dihydroxy compounds are aliphatic or aromatic dihydroxy compounds. Examples of suitable aromatic dihydroxy compounds are bisphenols, such as 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), tetraalkyl bisphenol A, 4,4- (meta-phenylene diisopropyl) diphenol (bisphenol M), 4,4- ( para-phenylenediisopropyl) diphenol, 1, 1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (BP-TMC), 2,2-bis (4-hydroxyphenyl) -2-phenylethane, 1 , 1-bis (4-hydroxyphenyl) cyclohexane (bisphenol-Z) and optionally mixtures thereof. The polycarbonates can be branched by using small amounts of branching agents. Suitable branching agents include phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) - heptane; 1, 3,5-tri (4-hydroxyphenyl) benzene; 1,1,1-tri (4-hydroxyphenyl) heptane; 1, 3,5-tri- (4-hydroxyphenyl) benzene; 1,1,1-tri- (4-hydroxyphenyl) -ethane; Tri- (4-hydroxyphenyl) -phenyl-methane, 2,2-bis [4,4-bis (4-hydroxyphenyl) -cyclohexyl] -propane; 2,4-bis- (4-hydroxyphenyl-isopropyl) -phenol; 2,6-bis (2-hydroxy-5'-methyl-benzyl) -4-methyl phenol; 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane; Hexa- (4- (4-hydroxyphenyl-isopropyl) -phenyl) -orthoterephthalate; Tetra (4-hydroxyphenyl) methane; Tetra (4- (4-hydroxyphenyl-isopropyl) -phenoxy) -methane; α, α ', α "-tris- (4-hydroxyphenyl) -1, 3,5-triisopropylbenzene; 2,4-dihydroxybenzoic acid; trimesic acid; cyanuric chloride; 3,3-bis (3-methyl-4-hydroxyphenyl) - 2-oxo-2,3-dihydroindole, 1,4-bis- (4 ', 4 "-dihydroxytriphenyl) -methyl) -benzene and especially 1, 1, 1-tri- (4-hydroxyphenyl) -ethane and bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole. For chain termination are, for example, phenols such as phenol, alkylphenols such as cresol and 4-tert-butylphenol, chlorophenol, bromophenol, cumylphenol or mixtures thereof. The proportion of chain terminators is usually 1 to 20 mol%, per mole of dihydroxy compound.

Another preferred embodiment of the present invention relates to a packaging material wherein the polymer is selected from polysulfones, polyethersulfones, polyetherketones and mixtures thereof.

Another preferred embodiment of the present invention relates to a packaging material wherein the polymer is selected from synthetic resins. The synthetic resins include crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins. Also included in the synthetic resins are drying and non-drying alkyd resins and unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also low-flammability halogen-containing modifications thereof. Furthermore, the synthetic resins include crosslinkable acrylic resins which are derived from substituted acrylates, such as epoxy acrylates, urethane acrylates or polyester acrylates. Furthermore, the synthetic resins include alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins and crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds. As is known, epoxy resins are formed by ring-opening crosslinking reaction of polybasic epoxides. Examples of epoxy resins include diglycidyl ethers of bisphenol-A or bisphenol F. They can be crosslinked with acid anhydrides or amines, with or without accelerators. The synthetic resins also include hydrocarbon resins, which usually have a molecular weight below 2,000. The hydrocarbon resins can be divided into three groups, the petroleum resins, terpene resins and coal tar resins. The hydrocarbon resins in the context of this invention, the hydrogenated modifications thereof and polyalkylenes are calculated.

A further preferred embodiment of the present invention relates to a packaging material, wherein the polymer is selected from natural polymers, such as cellulose, rubber, gelatin and chemically modified derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers, such as methylcellulose; as well as rosin and its derivatives. Cellulose is mainly used in blends with PET fibers in the clothing sector; also as artificial silk, linings, curtain fabrics, tire cord, cotton wool, dressings and sanitary articles. Cellulose esters are processed, for example, into electrical insulating films, photographic films and light and heat resistant thermoplastic binders for paints. Cellulose ethers serve as binders for clearcoat, inter alia for films.

A further preferred embodiment of the invention relates to a packaging material in which the polymer is selected from polymers derived from unsaturated alcohols and amines or from their acyl derivatives or acetals, such as polyvinyl acetate (PVAC) and polyvinyl alcohol (PVAL). In the reaction of polyvinyl alcohol with an aldehyde, polyvinyl acetals are formed, for example when reacted with formaldehyde polyvinylformale (PVFM) or with butyraldehyde, the polyvinyl butyrals (PVB). Polyvinyl compounds are not thermoplastic materials because of their low glass transition temperature, but polymer resins. They are used as coating compositions, for example for cheese coatings, lacquer and pigment binders, lacquer raw materials, glues, adhesives, chewing gum, films for the production of laminated glass and for many other purposes.

A further preferred embodiment of the invention relates to a packaging material, wherein the polymer is selected from polyamides (abbreviation PA) or copolyamides, which have as essential structural elements amide groups in the polymer main chain. Polyamides can be prepared, for example, by polycondensation from diamines and dicarboxylic acids or their derivatives. Suitable diamines are, for example, alkyldiamines such as C 2 -C 20 -alkyldiamines, eg. Hexamethylenediamine, or aromatic diamines such as Ce to C20 aromatic diamines, e.g. B. m- or the p-phenylenediamine or m-xylenediamine. Suitable dicarboxylic acids include aliphatic dicarboxylic acids or their derivatives, for example chlorides, such as C 2 - to C 20 -aliphatic dicarboxylic acids, for example sebacic acid, decanedicarboxylic acid or adipic acid or aromatic dicarboxylic acids, for example C 1 - to C 20 -aromatic dicarboxylic acids or derivatives thereof, for example chlorides, such as 2,6-naphthalenedicarboxylic acid, isophthalic acid or terephthalic acid. Examples of such polyamides are poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide, PA 6,6 (polyhexamethylene adipamide), PA 4,6 (polytetramethylene adipamide), PA 6,10 (polyhexamethylene sebacamide), PA 6/9, PA 6 / 12, PA 4/6, PA 12/12, where the first number always indicates the number of carbon atoms of the diamine and the second number indicates the number of carbon atoms of the dicarboxylic acid. Polyamides are also by polycondensation of amino acid, for example C2-C2o-amino acids such as 6-aminocaproic acid, 1 1-aminoundecanoic acid or by ring-opening polymerization of lactams, eg. B. caprolactam available. Examples of such polyamides are PA 4 (composed of 4-aminobutyric acid), PA 6 (composed of 6-aminohexanoic acid). For example, PA 11 is a polyundecanolactam and PA 12 is a polydodecanolactam. For polyamides, which are composed of only one monomer as in this case, the number after the abbreviation PA indicates the number of carbon atoms of the monomer.

Polyamides may optionally be prepared with an elastomer as a modifier. Suitable copolymamides are, for example, block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Also suitable are polyamides or copolyamides modified with EPDM or ABS and polyamides condensed during processing (RIM polyamide systems).

A further preferred embodiment of the present invention relates to a packaging material, wherein the polymer is selected from polymers derived from α, β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates; Polymethyl methacrylates (PMMA), polyacrylamides (PAA) and polyacrylonitriles (PAC), impact modified with butyl acetate. As is known, polyacrylic acids are formed by polymerization of acrylic acid. The polymerization can be carried out as a solution polymerization in water, as a precipitation polymerization, for example in benzene, or as a suspension polymerization.

Polyacrylic acid is used in the form of its salts as a thickener and in aqueous media for coatings. Acrylic acid and its copolymers with acrylamide are used as suspension aids for pigments, as flocculants in water treatment, as drilling aids in mining, as paper auxiliaries, as adhesives for metal / plastic compounds and for many other purposes. Polyacrylate esters are mainly used as binders for paints and varnishes, in the paper industry in coating slips and as binders and sizing agents, for the finishing of textiles, in adhesives and sealants, as leather auxiliaries, as elastomers and for many other purposes. A large field of application for PMMA is the use as a hardening component in binders of coating resins. In combination with acrylates, it provides high-quality coatings that are characterized by their durability, film toughness, gloss and weather resistance. Such resins are used in primers and coatings, emulsion paints and varnishes. PAA is used as a clarifier for fruit juices, as a crosslinker in coatings, in adhesives and many other applications.

A further preferred embodiment of the present invention relates to a packaging material, wherein the polymer is selected from copolymers of the monomers mentioned in the above paragraph with each other or with other unsaturated monomers such as acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / inyl halide copolymers or acrylonitrile / alkyl methacrylate / butadiene terpolymers.

Another preferred embodiment of the present invention relates to a packaging material wherein the polymer is selected from polystyrene, poly (p-methylstyrene), poly (α-methylstyrene), copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives or graft copolymers of styrene or α methyl styrene.

Unmodified styrenic polymers can be processed into foams that are used in construction and packaging. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives include styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; High impact strength blends of styrene copolymers and other polymer, e.g. a polyacrylate, a diene polymer or an ethylene / propylene / diene terpolymer; and block copolymers of styrene, such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

Graft copolymers of styrene or α-methylstyrene, e.g. Styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; Styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; Styrene and maleimide on polybutadiene; Styrene and alkyl acrylates or methacrylates on polybutadiene; Styrene and acrylonitrile on ethylene / propylene / diene terpolymers; Styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate / butadiene copolymers, and mixtures thereof with polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles, e.g. the copolymer blends known as ABS, MBS, ASA or AES polymers.

Another preferred embodiment of the present invention relates to a packaging material wherein the polymer is a polymer blend. The term "polymer blend" is understood to mean a mixture of two or more polymers or copolymers, and polymer blends serve to improve the properties of the base component.

Examples of polymer blends include PP / EPDM, polyamide / EPDM or ABS,

PVC / EA / A, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / Acrylate, POM / Thermoplastic PUR, PC / Thermoplastic PUR, POM / Acrylates, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

Acrylonitrile-butadiene-styrene copolymers (ABS) are thermoplastic or elastic polymer blends. They are prepared by graft polymerization of the three base monomers acrylonitrile, butadiene and styrene in an emulsion polymerization process or bulk polymerization process. The properties of ABS can be controlled via the proportions of the monomers used.

The stabilizer composition used in accordance with the invention may optionally be used together with at least one light stabilizer which absorbs light radiation in the UV-A and / or UV-B range and / or other (co) stabilizers in the packaging materials. Of course, the additionally used light stabilizer as well as optionally used (co) stabilizers must be compatible with the stabilizer composition used according to the invention. Preferably, they are colorless in the visible range or have only a slight intrinsic color. The optionally used light stabilizers or (co) stabilizers preferably have high migration stability and temperature stability. Suitable light stabilizers and further (co) stabilizers are selected, for example, from groups a) to s):

a) 4,4-diarylbutadienes, b) cinnamic acid esters, c) benzotriazoles, d) hydroxybenzophenones, e) diphenylcyanoacrylates, f) oxamides (oxalic acid diamides), g) 2-phenyl-1,3,5-triazines; h) antioxidants, i) nickel compounds j) sterically hindered amines, k) metal deactivators, l) phosphites and phosphonites, m) hydroxylamines, n) nitrones, o) amine oxides,

P) benzofuranones and indolinones, q) thiosynergists, r) peroxide-destroying compounds, s) basic costabilizers.

The group a) of the 4,4-diarylbutadienes include, for example, compounds of the formula A.

The compounds are known from EP-A-916 335. The substituents Rio and / or

Rn is preferably d-Cs-alkyl and Cs-Cs-cycloalkyl.

The group b) of the cinnamic acid esters includes, for example, isoamyl 4-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate, methyl α-methoxycarbonyl cinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano- β-methyl-p-methoxy cinnamate and methyl α-methoxycarbonyl-p-methoxycinnamate.

The group c) of the benzotriazoles includes, for example, 2- (2'-hydroxyphenyl) benzotriazoles, such as 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-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5 chloro-benzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl) -benzotriazole, 2- (2'-hydroxy-4'-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-chloro-benzotriazole, 2- (3'-tert-butyl-5' - [2- (2-ethylhexyloxy) - carbonylethyl] -2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-Butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2 -methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-5' - [ 2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole; 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (3'-tert-butyl-2 '-hydroxy-5' - (2-isooctyloxycarbonylethyl) -phenylbenzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl-phenol] the product of the esterification of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300; [R-CH ₂ CH ₂ -COO (CH ₂ ) 3] 2, with R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl-phenyl and mixtures thereof.

The group d) of the hydroxybenzophenones include, for example, 2-hydroxybenzophenones, such as 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2 ', 4,4' Tetrahydroxybenzo-phenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4- (2-ethylhexyloxy) benzophenone, 2-hydroxy 4- (n-octyloxy) benzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-3-carboxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its sodium salt, 2,2'- Dihydroxy-4,4'-dimethoxybenzophenone-5,5'-bisulfonic acid and its sodium salt.

The group e) of the diphenylcyanoacrylates includes, for example, ethyl-2-cyano-3,3-diphenylacrylate, which is obtainable, for example, commercially under the name Uvinul® 3035 from BASF AG, Ludwigshafen, 2-ethylhexyl-2-cyano-3, 3-diphenylacrylate, which is commercially available, for example, as Uvinul® 3039 from BASF AG, Ludwigshafen, and 1, 3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2 bis {[2'-cyano-3 ', 3'-diphenyl-acryloyl) oxy] methyl} propane, which is available, for example, commercially under the name Uvinul® 3030 Fa. BASF AG, Ludwigshafen.

The group f) of the oxamides includes, for example, 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butyloxanilide, 2,2'-didodecyloxy-5 , 5'-di-tert-butyloxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethyl-oxanilide and its Mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of ortho, para-methoxy-disubstituted oxanilides and mixtures of ortho and para-ethoxy disubstituted oxanilides.

Group g) of 2-phenyl-1,3,5-triazines includes, for example, 2- (2-hydroxyphenyl) -1,3,5-triazines such as 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2,4-dihydroxyphenyl ) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4- dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4 -dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) - 1, 3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) -phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5 triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -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) -4- 2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -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 and 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine ,

The group h) of the antioxidants include, for example: h.1) 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, unbranched or in the side chain branched nonylphenols such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1-methylundec-1-yl) -phenol, 2,4-

Dimethyl 6- (1-methylheptadec-1-yl) phenol, 2,4-dimethyl-6- (1-methyltridec-1-yl) phenol and mixtures thereof.

h.2) alkylthiomethylphenols such as, for example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-

Di-dodecylthiomethyl-4-nonylphenol.

h.3) hydroquinones and alkylated hydroquinones such as, for example, 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl 4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert Butyl 4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

h.4) tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

h.5) Hydroxylated thiodiphenyl ethers such as, for example, 2,2'-thio-bis (6-tert-butyl-4-methylphenol), 2,2'-thio-bis (4-octylphenol), 4,4'-thio bis (6-tert-butyl-3- methylphenol), 4,4'-thio-bis (6-tert-butyl-2-methylphenol), 4,4'-thio-bis (3,6-di-sec-amylphenol), 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.

h.6) alkylidene bisphenols such as, for example, 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol ), 2,2'-methylene bis [4-methyl

6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2 'Methylene-bis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (6) tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) - 4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1, 1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1, 1, 3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis- [3,3-bis (3-tert-butyl-4-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3 ') tert-butyl-2-hydroxy-5-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2, 2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1 , 1, 5,5-Tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) -pentane.

h.7) benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy -3,5-di-tert-butylbenzylmercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, 1, 3,5-tri- (3,5-di-tert-butyl) 4-hydroxybenzyl) -2,4,6-trimethylbenzene,

Di- (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetic acid isooctyl ester, bis (4-tert-butyl-3-hydroxybenzyl) 2,6-dimethylbenzyl) dithiol terephthalate, 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, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester and 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester, calcium salt.

h.8) Hydroxybenzylated malonates such as dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy 5-methylbenzyl) malonate, di-dodecylmercaptoethyl 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. h.9) hydroxybenzyl aromatics 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.

h.10) 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, 3,5-tιϊazin, 1, 3,5-tris (3 , 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1, 3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1, 3,5-triazine, 1, 3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro -1, 3,5-triazine, 1, 3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

h.11) benzyl phosphonates such as, for example, dimethyl 2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate ((3,5-bis (1 , 1-dimethylethyl) -4-hydroxyphenyl) methyl) phosphonic acid diethyl ester), dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of the 3 , 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.

h.12) acylaminophenols such as 4-hydroxy-lauric acid anilide, 4-hydroxystearic anilide, 2,4-bis-octylmercapto-6- (3,5-tert-di-butyl-4-hydroxyanilino) -s-triazine and octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbamate.

h.13) esters of ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols such. With 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) oxalic acid diamide,

3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

h.14) esters of ß- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, such as. With 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-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

h.15) esters of ß- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols such. With 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) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

h.16) esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols, such as. With 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) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

h.17) amides of ß- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, such as. B. N ₁ N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N ₁ N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hydrazine, N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl ] -propionyloxy) ethyl] -oxamide (eg Naugard® XL-1 from Uni-royal).

h.18) ascorbic acid (vitamin C)

h.19) Amine antioxidants, 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'-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'-dimethyl-N, N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-butyl) Octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-di-tert-butyl octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2 , 4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1, 2-bis - [(2-methylphenyl) amino] ethane, 1, 2

Bis (phenylamino) -propane, (o-tolyl) -biguanide, bis [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, mixture of mono- and dialkylated nonyldiphenylamines, mixture of mono- and dialkylated dodecyldiphenylamines, mixture of mono- and dialkylated isopropyl / isohexyl-diphenylamines, mixture of mono- and di- dialkylated tert-Butyldiphenylaminen, 2,3-dihydro-3,3-dimethyl-4H-1, 4-benzothiazine, phenothiazine, mixture of mono- and dialkylated tert-butyl / tert-octyl-phenothiazines, mixture of mono- and dialkylated tert Octylphenothiazines, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis- (2,2,6,6-tetramethyl- piperidin-4-yl) hexamethylenediamine, bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6 Tetramethylpiperidin-4-ol, the dimethylsuccinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol [CAS No. 65447-77-0], (for example, Tinuvin® 622 from Ciba Specialty Chemicals, Inc.), polymer based on 2,2,4,4-tetramethyl-7-oxa-3,20-diazo-dispiro [ 5.1.11.2] -heneicosan-21-one and epichlorohydrin [CAS No .: 202483-55-4], (for example Hostavin® N30 from Clariant, Germany.).

To group i) of the nickel compounds include, for example, nickel complexes of 2,2'-thio-bis [4- (1,1,3,3-tetramethylbutyl) phenol], such as the 1: 1 or 1: 2 complex, optionally with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonsäuremonoalkylester such. As the methyl or ethyl esters, nickel complexes of ketoximes such. For example, from 2-hydroxy-4-methylphenylundecylketoxim, nickel complex of 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with additional ligands.

The group j) of sterically hindered amines include, for example, 4-hydroxy-2, 2,6,6-tetramethylpiperidine, 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-benzyl-4-hydroxy 2,2,2,6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1, 2,2,6,6 - pentamethyl-4-piperidyl) -n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate (n-butyl-3,5-di-tert-butyl-4-hydroxy-benzyl-malonic acid bis ( 1, 2,2,6,6-pentamethylpiperidyl) ester), Condensation product of 1 - (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N ₁ 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-butane-tetracarboxylate, 1,1 '- (1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), 4-Benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1, 2,2,6, 6-pentamethylpiperidyl) -2-n-butyl 2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4- dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, 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, condensation product of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and formic acid ester (CAS no. 124172-53-8, eg Uvinul® 4050H from BASF AG, Ludwigshafen), condensation product of 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1, 3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, condensation product of 2-chloro-4,6-di- (4-n-butylamino-1,2,6,6,6-pentamethylpiperidyl) - 1, 3,5-triazine and 1, 2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane -2,4-dione, 3-dodecyl-1 - (2,2,6, 6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1, 2,2,6 , 6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, condensation product of N, N'-bis (2,2 , 6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensation product of 1, 2-bis (3-aminopropylamino) ethane and 2, 4, 6 Trichloro-1, 3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1, 2,2,6, 6-pentamethyl-4-piperidyl) -n-dodecyl-succinimide, 2- Undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro [4,5] decane, reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1 - oxa-3,8-diaza-4-oxospiro [4,5] decane and epichlorohydrin, 1,1-bis (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) ethene, N, N'-bis-formyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, diester of 4-methoxy-methylene-malonic acid with 1, 2, 2,6,6-Pentamethyl-4-hydroxypiperidine, poly [methylpropyl-3-oxo-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, reaction product of maleic anhydride-α-olefin copolymer and 2,2,6,6-tetramethyl-4-aminopiperidine or 1, 2,2,6,6-pentamethyl-4-aminopiperidine, copolymers of (partially) N-piperidin-4-yl substituted maleimide and a mixture of α-olefins such. Uvinul® 5050H (BASF AG), 1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 1- (2-hydroxy-2-methylpropoxy) -4- hexadecanoyloxy-2, 2,6,6-tetramethylpiperidine, the reaction product of 1-oxyl-4-hydroxy-2, 2,6,6-tetramethylpiperidine and a carbon radical of t-Amyl alcohol, 1- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 1- (2-hydroxy-2-methylpropoxy) -4oxo-2,2,6, 6-tetramethylpiperidine, bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1- (2-hydroxy-2-methylpropoxy) -2, 2,6,6-tetramethylpiperidin-4-yl) adipate, bis (1- (2-hydroxy-2-methylpropoxy) -2, 2,6,6-tetramethylpiperidin-4-yl) succinate, bis (1- (2 -hydroxy-2-methylpropoxy) -2,6,6,6-tetramethylpiperidin-4-yl) glutarate, 2,4-bis {N - (2-hydroxy-2-methylpropoxy) -2,2,6, 6-tetramethylpiperidin-4-yl] -N-butylamino} -6- (2-hydroxyethylamino) -s-tιϊazine, N, N'-bis-formyl-N, N'-bis (1, 2,2, 6,6-pentamethyl-4-piperidyl) -hexamethylenediamine, hexahydro-2,6-bis (2,2,6,6-tetramethyl-4-piperidyl) -1H, 4H, 5H, 8H-2,3a, 4a , 6,7a, 8a-hexaazacyclopenta [def] fluorene-4,8-dione (eg Uvinul® 4049 from BASF AG, Ludwigshafen), poly [[6 - [(1, 1, 3,3-) tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino] 1,6-hexanediyl [(2,2,6, 6-tetramethyl 4-piperidinyl) imino]]) [CAS No. 71878-19-8], N, N ', N ", N"' - tetrakis {4,6-bis [butyl- (N-methyl-2,2 , 6,6-tetramethylpiperidin-4-yl) amino] triazin-2-yl} -4,7-diazadecane-l, 10-diamine (CAS No. 106990-43-6) (e.g. Chimassorb 119 from Ciba Specialty Chemicals, Inc., Switzerland).

The group k) of the metal deactivators includes, for example, N, N'-diphenyloxalic diamide, N-salicylal-N'-salicyloyl-hydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5 di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2,4-triazole,

Bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N, N'-diacetyl adipic dihydrazide, N, N'-bis (salicyloyl) oxalic dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide.

The group I) of the phosphites and phosphonites include, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2 , 4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite , Bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis- (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isoctyloxy-2,4, 8,10-tetra-tert-butyl-dibenz [d, f] [1, 3,2] dioxaphosphepin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzene [d, g] [1, 3,2] dioxaphosphocine, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2,2 ', 2 "-nitrilo [triethyl-tris (3,3', 5,5'-tetra-tert-butyl) butyl-1, 1'-biphenyl-2,2'-diyl) phosphite], 2- (ethylhexyl) - (3,3 ', 5,5'-tetra-tert-butyl-1, 1'-biphenyl-2 , 2'-diyl) phosphite. M for group) of the hydroxylamines includes for example N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N ₁ N- ditetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecyl Hydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N-methyl-N-octadecylhydroxylamine and N, N-dialkylhydroxylamine from hydrogenated tallow fatty amines.

The group n) of the nitrenes includes, for example, N-benzyl-α-phenylnitrone, N-ethyl-α-methylnitrone, N-octyl-α-heptylnitrone, N-lauryl-α-undecylnitrone, N-tetradecyl-α-tridecylnitrone, N Hexadecyl-α-pentadecylnitrone, N-octadecyl-α-heptadecylnitrone, N-hexadecyl-α-heptadecylnitrone, N-octadecyl-α-pentadecylnitrone, N-heptadecyl-α-heptadecylnitrone, N-octadecyl-α-hexadecylnitrone, N-methyl -α-heptadecyl nitrone and nitrenes derived from N, N-dialkylhydroxylamines prepared from hydrogenated tallow fatty acids.

The group o) of the amine oxides includes, for example, amine oxide derivatives as disclosed in U.S. Pat. Nos. 5,844,029 and 5,880,191, didecylmethylamine oxide, tridecylamine oxide, tridodecylamine oxide and trihexadecylamine oxide.

The group p) of the benzofuranones and indolinones include, for example, those disclosed in U.S. Patents 4,325,863; 4,338,244; 5,175,312; 5,216,052; 5,252,643; in DE 431661 1; in DE 4316622; in DE 4316876; in EP 0589839 or EP 0591102 or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2 (3H) -one, 5,7-di-tert-butyl -3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2 (3H) -one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl ) benzofuran-2 (3H) -one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) -benzofuran-2 (3H) -one, 3- (4-acetoxy-3,5-dimethylphenyl) 5,7-di-tert-butylbenzofuran-2 (3H) -one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2 (3H) -on, 3- (3,4-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2 (3H) -one, Irganox® HP-136 from Ciba Specialty Chemicals, and 3- (2,3 -Dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2 (3H) -one.

The group q) of thiosynergists includes, for example, dilauryl thiodipropionate or distearyl thiodipropionate.

The group r) of the peroxide-destroying compounds include, for example, esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (β dodecylmercapto) propionate. The group s) of basic costabilizers include, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, higher fatty acid alkali and alkaline earth salts, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony catecholate or zinc catechinate.

The stabilizer composition used according to the invention may optionally be used together with other additives and additives (group t) in the polymer composition. Suitable additives of group t) include nucleating agents, fillers and reinforcing agents, plasticizers, lubricants, emulsifiers, colorants, rheology additives, flame retardants, antistatic agents, biocides and blowing agents.

Suitable nucleating agents are, for example, inorganic substances, such as talc, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and the salts thereof, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). Particularly preferred are 1, 3-; 2,4-bis (3 ', 4'-dimethylbenzylidene) sorbitol, 1, 3; 2,4-di (paramethyldibenzylidene) sorbitol and 1,3-2,4-di (benzylidene) sorbitol.

Suitable fillers or reinforcing agents include, for example, calcium carbonate, silicates, talc, mica, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers. Examples of fibrous or pulverulent fillers are also carbon or glass fibers in the form of glass fabrics, glass mats or glass silk rovings, chopped glass, glass beads and wollstonite. The incorporation of glass fibers can take place both in the form of short glass fibers and in the form of continuous fibers (rovings).

Suitable antistatic agents are, for example, amine derivatives such as N, N-bis (hydroxyalkyl) alkylamines or -alkyleneamines, polyethylene glycol esters and ethers, ethoxylated carboxylic acid esters and amides and glycerol mono- and distearates, and mixtures thereof.

The term colorant includes both dyes and pigments. Preferably, the colorant is a pigment. The pigment can be an inorganic or organic Be pigment. Also to be regarded as colorants are organic compounds which have fluorescence in the visible part of the electromagnetic spectrum, such as fluorescent dyes. The colorant may also have other properties such as electrical conductivity or be magnetically shielding.

Examples of suitable inorganic color pigments are white pigments such as titanium dioxide in its three modifications rutile, anatase or brookite, lead white, zinc white, zinc sulfide or lithopone; Black pigments such as carbon black, iron oxide black, iron manganese black or spinel black; Colored pigments such as chromium oxide, chromium oxide green, cobalt green or ultramarine blue, cobalt blue, iron blue, milori blue, ultramarine blue or manganese blue, ultramarine violet or cobalt and manganese violet, iron oxide red, cadmium sulphoselenide, molybdate red or ultramarine red; Iron oxide brown, mixed brown, spinel and corundum phases or chrome orange; Iron oxide yellow, nickel titanium yellow, chromium titanium yellow, cadmium sulfide, cadmium zinc sulfide, chrome yellow, zinc yellow, alkaline earth chromate, Naples yellow; Bismuth vanadate, effect pigments such as interference pigments and luster pigments.

Suitable inorganic pigments include: Pigment White 6, Pigment White 7, Pigment Black 7, Pigment Black 1 1, Pigment Black 22, Pigment Black 27/30, Pigment Yellow 34, Pigment Yellow 35/37, Pigment Yellow 42, Pigment Yellow 53, Pigment Brown 24, Pigment Yellow 1 19, Pigment Yellow 184, Pigment Orange 20, Pigment Orange 75, Pigment Brown 6, Pigment Brown 29, Pigment Brown 31, Pigment Yellow 164, Pigment Red 101, Pigment Red 104, Pigment Red 108 Pigment Red 265, Pigment Violet 15, Pigment Blue 28/36, Pigment Blue 29, Pigment Green 17, Pigment Green 26/50.

Examples of suitable organic pigments include aniline black, Anthrapyrimidinpig- elements, elements azomethine pigments, anthraquinone pigments, monoazo pigments, Bisazopig-, benzimidazolone pigments, quinacridone pigments, quinophthalone pigments, diketone topyrrolopyrrolpigmente, dioxazine, flavanthrone, Indanthronpig- elements, elements Indolinonpigmente, isoindoline pigments, isoindolinone pigments, Thioindigopig-, Metal complex pigments, perinone pigments, perylene pigments, pyranthrone pigments, phthalocyanine pigments, thioindigo pigments, triaryl carbonium pigments or metal complex pigments.

Suitable organic pigments include: Examples of organic pigments are: Cl. (Color Index) Pigment Violet 29, Cl. Pigment Yellow 93, Cl. Pigment Yellow 95, Cl. Pigment Yellow 138, Cl. Pigment Yellow 139, Cl. Pigment Yellow 155, Cl. Pigment Yellow 162, Cl. Pigment Yellow 168, Cl. Pigment Yellow 180, Cl. Pigment Yellow 183, Cl. Pigment Red 44, Cl. Pigment Red 149, Cl. Pigment Red 170, Cl. Pigment Red 178, Cl. Pigment Red 179, Cl. Pigment Red 202, Cl. Pigment Red 214, Cl. Pigment Red 254, Cl. Pigment Red 264, Cl. Pigment Red 272, Cl. Pigment Red 48: 2, Cl. Pigment Red 48: 3, Cl. Pigment Red 53: 1, Cl. Pigment Red 57: 1, Cl. Pigment Green 7, Cl. Pigment Blue 15: 1, Cl. Pigment Blue 15: 3, Cl. Pigment Blue 15: 4, Cl. Pigment Violet 19.

Some of the pigments mentioned, such as, for example, carbon black or titanium dioxide, can also function as fillers or reinforcing agents and / or as nucleating agents.

Examples of suitable dyes are: azo dyes, pyrazolone dyes, anthraquinone dyes, perinone dyes, perylene dyes, indigo and thioindigo dyes and azomethine dyes.

Examples of suitable flame retardants are organic chlorine and bromine compounds alone or in combination with antimony trioxide, phosphorus compounds such as phosphate esters, aluminum hydroxide or boron compounds.

Examples of suitable propellants are propane, butane or pentane.

The stabilizer composition used according to the invention or the sum of all the stabilizer compositions used according to the invention can be added to the packaging material in customary amounts, generally in a concentration of from 0.01 to 5% by weight. The stabilizer composition used according to the invention is preferably added in an amount of 0.02 to 2.5% by weight and more preferably 0.1 to 1.0% by weight, based on the total weight of the plastic.

The total weight of the plastic is understood as meaning the weight of the stabilizer composition used in accordance with the invention, and optionally plastic mixed with further stabilizers and costabilizers (plastic + sum of all (co) stabilizers + sum of all other additives).

The compounds from groups a) to s) are used, with the exception of the benzofuranones of group p), in customary amounts, for example in amounts of

0.0001 to 10 wt .-%, preferably 0.01 to 1 wt .-%, based on the total weight of the plastic. The additives of group t) are used in the usual amounts. Usually, they are used in an amount of 0 to 60 wt .-%, based on the total weight of the plastic.

The stabilizer composition used according to the invention can also be added to the packaging materials, usually a plastic, in the form of a premix (masterbatch or compound) containing at least one stabilizer composition used according to the invention in a concentration of 1 to 20% by weight. Furthermore, the premix may contain the abovementioned compounds of groups a) to s) and other additives of group t).

The stabilizer composition used according to the invention and, if present, the compounds of groups a) to s) and / or the other additives of group t) are added to the plastic. The addition takes place in a customary manner, for example by mixing with the plastic. Thus, the stabilizer composition used according to the invention and, if appropriate, the further stabilizers can also be added to the starting monomer and the mixture of monomers and stabilizers can be polymerized. Likewise, it is possible to add the stabilizer composition used according to the invention and optionally the compounds of groups a) to s) and / or the other additives of group t) during the polymerization of the monomers. The prerequisite for an addition before or during the polymerization is that the stabilizer composition used according to the invention and optionally the compounds of groups a) to s) and / or the other additives of group t) are stable under the polymerization conditions, ie not or only little decompose.

Preference is given to adding the stabilizer composition used according to the invention and optionally the compounds of groups a) to s) and / or the other additives of group t) to the finished plastic. This is done in the usual way according to known mixing method, for example, with melting at temperatures of 150 to 300 ° C. However, the components can also be mixed "cold" without melting and the powdery or granular mixture is first melted and homogenized during processing.

It is understood that the components (A) to (D) of the stabilizer composition used according to the invention, and optionally the compounds of groups a) to s) and / or the other additives of group t) together or separately, at once , in portions or continuously, over time constant or along a gradient. For example, you can have one Add part of the stabilizer composition according to the invention already during the polymerization of the monomers and add the remainder only to the finished polymer, or you can add the entire amount of the stabilizer composition used in the invention to the finished polymer.

The blending is preferably carried out in a conventional extruder, wherein the components can be mixed or introduced individually, for example completely through a funnel, into the extruder or even later introduced at a later point of the extruder to the molten or solid product in the extruder. For example, single or twin-screw extruders are particularly suitable for melt extrusion. A twin-screw extruder is preferred.

The polymer compositions obtained may for example be pelletized or granulated, or processed by well-known methods, for example by extrusion, injection molding, foaming with blowing agents, thermoforming, blow molding, blown film forming or calendering.

From the polymer compositions can be produced moldings of all kinds, for example, packaging and films, for example, for textiles, especially packaging for cosmetics, perfumes and pharmaceuticals and packaging and films for food, beverage bottles or packaging for cleaning agents. Furthermore, stretch films can be produced from the polymer compositions. Stretch films can be used, for example, as outer packaging for wrapping already packaged goods. The overwrapping then protects primarily the packaging of the product from the damaging influence of light, heat and / or oxygen, for example, before fading.

In principle, each product can be protected by a package containing the stabilizer composition used according to the invention. Preferably, the product to be protected is selected from among cosmetic products, pharmaceuticals, perfumes, foods and cleansers. Suitable cosmetic products include soap, body lotion, skin cream, shower bath, bubble bath, body spray, make-up, eyeliner, mascara, blush, lipstick, hair shampoo, hair conditioner, hair gel, hair wax, hair lotions, nail polish, nail polish remover, etc. To suitable pharmaceutical products include pharmaceutical compositions or drugs in the form of tablets, pills, dragees, suppositories, solutions, dry juice, suspensions and the like. Suitable foods include carbonated and non-carbonated soft drinks like lemonade, fizzy drinks like beer or fruit juice / fizzy Water, non-carbonated beverages such as wine, fruit juice, tea or coffee, fruit, meat, sausage, dairy products such as milk, yoghurt, butter or cheese, animal and vegetable fats, bakery products, pasta, spices, sauces, pastes, pesto, funds, Marks, Ketchups, dressings, etc. Suitable cleaning products include household cleaners and industrial cleaners.

The stabilizer composition used according to the invention is particularly preferably used in thermoplastic molding compositions containing polyolefins, for agricultural films and packaging films, in biaxially oriented polypropylene for stretch wrap films, in polyethylene terephthalate or polyethylene naphthalate for bottles and other packaging containers, in polystyrene and polyvinyl chloride for blister products. packaging and other packaging containers, in polycarbonate for bottles, flasks and other packaging containers, in polyvinyl chloride for packaging containers and films or in polyvinyl alcohol for the production of films.

Optionally, the films of different polymers can be combined by lamination or as extrusion laminates together to form composite films. By mono- or biaxial stretching, if necessary, the properties can be improved. This is used for example for the production of shrink films. Shrink foils can be produced, for example, from polyethylene terephthalate, polyethylene, polyvinylidene chloride or polyvinyl chloride.

The packaging produced from thermoplastic molding compositions using the stabilizer composition according to the invention is distinguished by special quality features. In comparison with the packaging stabilized with the comparative composition, damage to the packaged products by oxygen and / or light and / or heat takes place to a lesser extent.

The following examples are intended to illustrate the invention without, however, limiting it.

The stabilizers (A) used according to the invention can be synthesized in a two-stage process. In the first stage, the synthesis of the cyanine cations with conventional anions, such as iodide takes place. The synthesis is known in principle to a person skilled in the art and can be carried out analogously to syntheses known from the literature, for example according to the instructions of K. Vankataraman "The Chemistry of Synthetic Dyes", Academic Press, New York, 1952, Vol. II and H. Zollinger "Color Chemistry: Synthesis, Properties, and Applications of Organic Dyes and Pigments", Weinheim, Wiley-VCH, 2003. In a second step, the customary anion is exchanged for an anion used according to the invention.

I. Preparation Examples

1st stage: Synthesis of cyanine cations with common anions

The following is an example of the synthesis of 2- [2- [2- [1,3-dihydro-1-ethyl-3,3-dimethyl-2H-indol-2-ylidene) ethylidene] -1-cyclohexene. 1 -yl] ethenyl] -1-ethyl-3,3-dimethyl-3H-indolium iodide described.

10 g (0.032 mol) of 3-ethyl-1, 1, 2-trimethylindolium iodide and 2.7 g (0.016 mol) of 3-hydroxymethylene-cyclohex-1-en-carbaldehyde were dissolved in a mixture of 105 ml of butanol and 45 ml Submitted toluene. It was heated to 110 ° C and the resulting water was removed. After stirring for five hours, it was cooled to room temperature. After concentrating the solution, methyl tert-butyl ether was added. The resulting crystals were filtered off with suction and washed with methyl tert-butyl ether. There were obtained 9.4 g of crystals and dried at 50 ° C in vacuo (mp 235 ° C).

In an analogous manner other cyanine cations were synthesized using customary starting compounds using customary anions.

2nd stage: General procedure for the preparation of stabilizers (A) used according to the invention by exchanging the anion

2- [2- [2- [2- (1,3-dihydro-1-ethyl-3,3-dimethyl-2H-indol-2-ylidene) ethylidene] -1-cyclohexene-1-yl] ethenyl] 1-ethyl-3,3-dimethyl-3H-indolium dodecylsulfonate (A1)

Compound A1 was prepared as follows: 0.003 mol (1.6 g) of the previously prepared iodide of 2- [2- [2- [2- (1,3-dihydro-1-ethyl-3,3-dimethyl-2H -indol-2-ylidene) -ethylidene] -1-cyclohexen-1-yl] ethenyl] -1-ethyl-3,3-dimethyl-3H-indolium were added along with 0.009 mol (2.3 g) of Na dodecylsulfonate in 50 ml of dichloromethane submitted. 50 ml of water were added, stirred for 30 minutes at room temperature and finally the phases were separated. The organic phase was washed three times with 50 ml of water until no iodide was detectable in the wash water with silver nitrate solution. After drying the organic phase with sodium sulfate, the solvent was distilled off and the residue was dried at 50 ° C in vacuo. In an analogous manner, using other cyanine cations and corresponding salts of the desired anions, the following stabilizer compositions were prepared. The synthesized stabilizers (A) according to the invention are summarized in Table 1.

Table 1: Synthesized stabilizers according to the invention (A)

Compound cyanine cation anion

Compound cyanine cation anion

II. Application examples

11.1 oxygen uptake test

In a typical experiment, a stabilizer composition was dissolved or suspended in 30 ml of toluene as follows. The solution was in a gas-tight 100 ml screw-cap glass, which is connected via a hole in the lid with a gas burette. The temperature was monitored throughout the experiment because the volume is temperature dependent. The solution or suspension was exposed with a slide projector at a distance of about 5 cm. Over the course of the experiment, the oxygen consumption was read from the volume change detected by the gas burette and read after 60 minutes. The results are summarized in Table 2.

For the purpose of comparison, under the same conditions, pure toluene and a reaction solution containing a co-initiator (B1) represented by the following formula were obtained

and n-butyl acrylate or A7 + n-butyl acrylate examined.

Table 2: Oxygen uptake after 60 min

The measured volume change is a measure of the amount of oxygen absorbed. The photoinitiator compositions used according to the invention cause a significant volume reduction, i. the amount of oxygen absorbed is correspondingly higher.

II.2 incorporation of the photoinitiator in LDPE film

A first mixture of 1% of the compound A2 and 99% Lupolen® 1800 S (LDPE, Basell, Germany) was mixed thoroughly in a mixing vessel and on a Twin-screw extruder (Leistritz ZSE 18) at 180-190 ° C cylinder temperature, 300 r / min and a torque of 70% incorporated. The resulting polymer strand was granulated through a granulator to obtain granules 1.

In the same way, a second mixture of 1% B1 and 99% Lupolen® 1800 S (Basell, Germany) was processed into a polymer strand and granulated by means of a granulator to obtain granules 2.

Before the production of the films, the granules described above were dried separately in a circulating air dryer at 80 ° C. for 2 hours. To produce the films on a CoIMn blown film line, the same parts of the granules 1 and 2 were mixed and processed at 180 ° C cylinder temperature to a 100 micron thick film. The extrusion speed and take-up speed were adjusted so that the film thickness was about 100 μm.

There were obtained films with the stabilizer composition of the invention, which are advantageously suitable as packaging material.

Claims

claims

Use of a packaging material containing a stabilizer composition containing

(A) at least one stabilizer of at least one cyanine cation Cya ⁺ and at least one corresponding anion equivalent ¹ / _m An ^{m "} , wherein the cyanine cation is selected from compounds of the general formulas (I), (II), (IM), (IV), (V) or (VI),

wherein

n is 1 or 2; p is 0, 1, 2 or 3;

R ¹ and R ^{2 are} independently linear or branched, optionally substituted CrC ₂ o-alkyl radicals; R ³ and R ^{4 are} independently H, CF ₃ or CN;

R ⁵ for each repeat unit is independently selected from hydrogen, halogen, phenyl, phenyloxy, phenylthio, diphenylamino, pyridyl, a barbituric acid or a dimedone radical, where the phenyl and pyridyl radicals may optionally be substituted;

R ⁶ for each repeat unit is independently selected from H, CF ₃ or CN;

R ^{7 is} a hydrogen, halogen, phenyl, phenyloxy, phenylthio, diphenylamino, pyridyl, a barbituric acid or a dimedone radical, wherein the

Phenyl and pyridyl radicals may optionally be substituted;

R ⁸ and R ^{9 are} independently C (CH ₃ ) ₂ , oxygen, sulfur, NR ^a, or -CH = CH-, where R ^{a is} a linear or branched, optionally substituted dC ₂ o-alkyl radical; R ¹ , R ", R ¹ ", R ^IV , R ^V , R ^VI , R ^V ", R ^Vι ", R ^ιx , R ^x , R ^xι and R ^x "independently one or more, similar or different substituents are selected from hydrogen, halogen, -NO ₂ , -CN, alkyl, alkoxy, -SO ₂ CF ₃ , aryl or aryloxy;

and wherein the anion An ^{m "is} selected from halides, pseudohalides or anions of the general formula [AR ¹⁰ _k ] ^m" , in which

A is a polar ionic group; R ^{10 is} at least one nonpolar group which is independently selected from C ₆ -C ₃₀ -alkyl groups, C ₆ -C ₃₀ -

Cycloalkyl groups and (C ₃ -C ₃₀ alkyl) aryl groups; k is 1, 2 or 3; m is 1 or 2; and

(B) at least one co-stabilizer selected from alkyl-substituted boranate salts, sulfonium salts, iodonium salts, sulfones, peroxides, pyridine-N-oxides and halomethyltriazines,

for the protection of packaged products from the harmful effects of oxygen and / or light and / or heat.

2. Use according to claim 1, wherein the co-stabilizer (B) is a compound of the formula (VII)

with an associated counterion ¹ / _x cat ^{x +} ,

where x is 1 or 2;

Kat is an x-valent cation; z ¹ , z ² , z ³ and z ⁴ are each independently 0 or 1, the sum z ¹ + z ² + z ³ + z ^{4 being} 0, 1, 2 or 3;

Y ¹ , Y ² , Y ³ and Y ⁴ are each independently O, S or NR ¹⁷ ;

R ^13, R ^14, R ¹⁵ and R ¹⁶ each are independently selected from optionally substituted Ci-Ci ₈ alkyl, optionally substituted C ₂ -C ₈ alkyl which is selected by one or more heteroatoms or heteroatom-containing groups, ^b are O, S, and NR, wherein R ^b for Al- kyl, cycloalkyl or aryl, is interrupted, optionally substituted C ₆ - C ₄ aryl, optionally substituted C ₅ - Ci ₂ cycloalkyl, and optionally substituted five- - to six-membered heterocycloalkyl and / or heteroaryl radicals; and

C ₆ -C ₂ -cycloalkyl or C ₆ C ₁₈ alkyl, - - ₄ Ci is aryl, R ¹⁷ is hydrogen, Ci;

with the proviso that at least one of the radicals R ¹³ to R ¹⁶ is an optionally substituted Ci - Ci ₈ alkyl and at least one of the radicals R ¹³ to R ¹⁶ is an optionally substituted C ₆ - C ₄ aryl radical, where the radicals mentioned optionally may be substituted.

3. Use of a stabilizer composition according to claim 1 or 2, which contains as additional component (C) a transition metal complex or a salt of a transition metal.

4. Use of a stabilizer composition according to any one of the preceding claims, which contains as additional component (D) at least one ethylenically unsaturated compound.

5. Use according to one of the preceding claims, wherein the product to be protected is selected from cosmetic products, perfumes, pharmaceutical products, foods, textiles and cleaning products.

Use of a stabilizer composition as defined in any one of claims 1 to 4 in a packaging material containing at least one polymer or consisting of at least one polymer.

7. Use according to claim 6, wherein the polymer is selected from polyolefins, polyolefin copolymers, polytetrafluoroethylenes, ethylene-tetrafluoroethylene copolymers, polyvinyl chlorides, polyvinylidene chlorides, polyvinyl alcohols, polyvinyl esters, polyvinylalkanals, polyvinyl ketals, polyamides, polyimides, polycarbonates, polycarbonate blends , Polyesters, polyester blends, poly (meth) acrylates, poly (meth) acrylate-styrene copolymer blends, poly (meth) acrylate-polyvinylidene difluoride blends, polyurethanes, polystyrenes, styrene copolymers, polyethers, polyether ketones, polysulfones and mixtures from that.

8. Use according to claim 7, wherein the polyolefin is selected from homo- and copolymers of ethylene and homo- and copolymers of propylene.

9. Use according to claim 8 for the production of moldings, films and fibers.

10. The method according to claim 6, wherein the polymer used to produce a pack is a thermoplastic molding composition.

1 1. A packaging material containing an effective against the harmful effect of oxygen and / or light and / or heat amount of a stabilizer composition as defined in any one of claims 1 to 4.

12. A method of protection against the action of oxygen and / or light and / or heat sensitive products, in which at least partially with a packaging material containing at least one stabilizer composition as defined in any one of claims 1 to 4.