WO2010072768A1 - Uv absorber agglomerates - Google Patents

Abstract

The present invention relates to a polymer composition containing (i) at least one polyolefin in the continuous phase; and (ii) at least one amphiphilic additive which is present in the continuous phase at least in part in the form of spherical self-organized structures, and wherein the self-organized structures have a median diameter of less than 200 nm.

Description

 UV absorber agglomerates

description

The present invention relates to a polymer composition containing at least one polyolefin as the continuous phase and at least one amphiphilic additive, wherein the amphiphilic additive in the continuous phase is at least partially in the form of self-organizates. The amphiphilic additive is preferably a light stabilizer, in particular a sterically hindered amine, and stabilizes the polyolefin against external influences, in particular against degradation by heat, light,

Oxygen and / or chemical action. The polymer compositions find particular use for the production of moldings, films and fibers, especially for the production of agricultural films.

As is known, polyolefins, like all plastics, undergo degradation reactions under the action of light and / or oxygen, which lead to a deterioration of the polymer properties. When used outdoors, polyolefins are additionally damaged by external factors such as acid rain or acidic substances. The consequence is an irreversible deterioration of the chemical and / or physical properties of the polyolefins. By adding a stabilizer or stabilizer mixture, the occurrence of damage by the action of light and / or oxygen can generally be avoided or at least delayed.

Numerous stabilizers and stabilizer blends for polyolefins have been described, i.a. also hindered amines (Hindered Amine Stabilizer, HAS, also referred to below as HALS). Conventionally, prior art HAS compounds are 2,2,6,6-tetraalkylpiperidine derivatives. HAS compounds, due to their peroxide radical decomposing action, prevent the light-induced decomposition of polymers and polymer products. Thus, HAS stabilize polymers by trapping intermediately formed radicals, whereby a free radical scavenging cycle is assumed as the mechanism of action. The HAS compounds used for the stabilization can be monomeric as well as oligomeric. Here, oligomeric HAS compounds are particularly suitable because they are characterized by a low tendency to migrate in the polyolefin. WO 94/12544 describes certain maleimide-α-olefin copolymers having tetramethylpiperidinyl side groups which are effective stabilizers.

The light stabilizers known from the prior art are partly unsatisfactory in terms of their stabilizing effect and / or offer no long-term protection. Many sunscreens are not thermostable at the processing temperature of the polyolefin. Many light stabilizers also have low solubility in the application medium. The resulting crystallization of the sunscreen can cause clouding of the polymer. Another disadvantage is a lack of compatibility between light stabilizer and polyolefin, which leads to a phase separation between polyolefin and light stabilizer. The result is a migration of the light stabilizer in the near-surface layer of the polyolefin. From here, the light-protective agent can be dissolved out, for example by precipitation from the polyolefin. Another disadvantage of known stabilizers is their low sublimation resistance. Frequently, sunscreens also have low photochemical stability. Another disadvantage is a lack of stability of the sunscreen against environmental influences such as acid rain and / or chemicals, such as agrochemicals. For example, it is known that HAS compounds as well as their oxidation onsprodukte such. As hydroxylamines, by reaction with acid, for example in the form of acid rain, are deactivated. Another disadvantage is often the poor synthetic accessibility of the light stabilizer or its insufficient formulability. There is therefore still a need for stabilizers which have improved performance properties and / or are easier to produce.

It is therefore an object of the present invention to provide polymer compositions based on polyolefins which are largely insensitive to the action of heat, oxygen and light for long periods of time. Furthermore, a satisfactory protection against destruction by acid rain or compounds having a pk _s value (pKs = negative logarithm of the acid constant) of less than 15.74 should be achieved. Furthermore, the light stabilizers should be synthetically readily accessible, ensure long-lasting, high protection in the case of a small amount used and have a high resistance to migration.

According to the invention this object is achieved by a polymer composition containing

(i) at least one polyolefin as or in the continuous phase; and

(ii) at least one amphiphilic additive, which in the continuous phase is present at least partly in the form of spherical self-organisates and wherein the semi-structured materials have an average diameter of less than 200 nm.

The polymer composition according to the invention has a very good long-term stability to light, heat, oxygen and / or compounds having an acidic character.

A specific embodiment of the present invention is a polymer composition which additionally contains a metal salt of a C 7 -C 30 -carboxylic acid, preferably a metal salt of stearic acid or behenic acid. In a further specific embodiment, the polymer composition according to the invention contains at least one additive which is different from the amphiphilic additive ii) and is chosen from colorants, lubricants, antioxidants, light stabilizers, antistatics, flame retardants, nucleating agents, pigment dispersants, biocides and fillers and reinforcing agents.

Another object of the present invention relates to a process for the preparation of the polymer composition according to the invention, wherein the polyolefin plasticized and brings in the plasticized state with the amphiphilic additive ii) in intimate contact and at the same time or subsequently admits the optionally present additives.

Another object of the present invention relates to the use of the polymer composition according to the invention for the production of moldings, films and fibers, in particular for the production of agricultural films.

Another object of the present invention relates to an agricultural film containing or consisting of the polymer composition according to the invention.

Another object of the present invention relates to a method for plant culture, wherein (i) a crop at least partially surrounds with an agricultural film according to the invention; and

(ii) the cultivated plant is treated once or several times with an agrochemical, the agrochemical or its microbial metabolite having a pK _s -

Value less than 15.74 at 25 ⁰ C.

Another object of the present invention relates to the use of agricultural film in a plant culture which comes into contact with compounds having an acidic character.

Amphiphiles are molecules that possess both hydrophilic and lipophilic properties. In the context of the present invention, the term "amphiphilic additive" means a low or high molecular weight substance which has a polar, hydrophilic group at one end and a non-polar, hydrophobic group at the other end of the compound. In the context of the present invention, a single amphiphile is also referred to as "unimer".

The amphiphiles ii) used according to the invention are capable of forming "self-organisates" (self-assemblates). These selforganizates are aggregates formed by association, ie micelle-like structures. The formation of self-assemblies is likely without being bound by theory due to the fact that the polar group of the amphiphile strives not to come into contact with the nonpolar polyolefin which is contained in or forms the continuous phase. The self-organics then preferably have hydrophilic groups on the inside and hydrophobic groups on the outside. In other words, in the self-assemblies, the non-polar groups of the amphiphiles are preferably outwardly directed toward the polyolefin and protrude into the continuous phase. The non-polar group forms the nonpolar tail group. The polar, hydrophilic groups of the amphiphiles lie internally and form the polar head group, which is shielded by the non-polar tail of the nonpolar polyolefin. Without wishing to be bound by theory, it is believed that the amphiphiles are held together by intermolecular attractive forces such as van der Waals forces acting between the hydrophobic groups.

The self-organysates have a spherical structure. Under a spherical structure is understood within the scope of the invention, an approximately spherical structure, i. corresponding deviations of the selforganizates from the ideal spherical shape are also covered by the invention.

The self-organisates formed according to the invention are characterized in particular by the fact that no or only a small proportion of high molecular weight aggregates is formed.

For the structural characterization of the amphiphilic additive ii), for example, the static and dynamic light scattering is suitable, as explained in more detail below.

In the context of the present invention, the particle diameter is understood to mean the hydrodynamic diameter. The hydrodynamic diameter corresponds to the diameter of a hypothetical solid sphere, which has the same diffusion properties in a solvent as the particle described by the hydrodynamic diameter.

The average particle diameter is less than 200 nm. Specifically, the average particle diameter is less than 100 nm. Similar to low molecular weight soaps and fats, the self-organisates are referred to here and below as inverse micelles. Here and below, the self-assemblages formed from several unimers are also referred to as "multimers".

In the context of the present invention, the term "plastification" means the transition of a polyolefin from the solid to a flowable state by application of pressure and / or temperature. The application of pressure can For example, by intensive kneading or extrusion. The polyolefin is melted in a plasticizer unit. Examples of suitable plasticizing units are extruders, calenders or injection molding machines.

In the context of the present invention, the term "agrochemicals-Ne" means a chemical used in agriculture, preferably a fertilizer or crop protection agent.

In the context of the present invention is meant by the term "acidic connects fertil" a compound whose pKa is less than 15.74 at 25 ⁰ C.

In the context of the present invention, collective definitions are used in the definitions of the variables given in the formulas, which are generally representative of the respective substituents. The meaning C _n -C m indicates the particular possible number of carbon atoms in the respective substituent or substituent part.

In the context of the present invention, C 1 -C 6 -alkyl represents saturated, straight-chain or branched alkyl groups having 1 to 6 carbon atoms, e.g. C 1 -C 6 -alkyl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1, 1

Dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2 Ethyl butyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, and the like.

In the context of the present invention, C 16-C 32 -alkyl is saturated, straight-chain or branched alkyl groups having 16 to 32 carbon atoms, for example cetyl, stearyl (octadecyl), isostearyl, nonadecyl, arachidyl, behenyl, nonadecyl, ligno-ceryl, montanyl , Myricyl, etc.

In a preferred embodiment, the amphiphilic additive ii) is a light stabilizer or a mixture of light stabilizers.

In a particularly preferred embodiment, the amphiphilic additive ii) is a polymeric light stabilizer which contains in copolymerized form at least one α, β-ethylenically unsaturated compound having a sterically hindered amine group. The polymeric light stabilizer preferably additionally comprises at least one α-olefin in copolymerized form. Specifically, the amphiphilic additive ii) is a copolymer comprising copolymerized repeating units of an alpha-olefin and an alpha, beta-ethylenically unsaturated amine-side chain-hindered compound. In particular, the copolymer is an oligomeric compound, the repeat units of the formula (I)

contains, in which

R ^{1 is} hydrogen;

R ^{2 is} hydrogen or C ₁ -C ₃ 2-alkyl;

R ^{3 is} hydrogen or C ¹ -C 32 alkyl; R ⁴ is Ci6-C _{3 is} 2-alkyl; R ⁵ for a tetramethylpiperidinyl radical of the formula (II)

stands; in which

R ^{6 is} hydrogen, C ₁ -C ₆ -alkyl or an O-radical (-O), where not more than 60 mol% of the radicals R ⁶ may be an O-radical; and

L ^{1 is} -C (= O) O-, -OC (= O) -, -O- or -C (= O) N (R ⁷ ) -, preferably -C (= O) O-, wherein R ^{7 is} hydrogen or C 1 -C 6 -alkyl,

or

R ¹ together with UR ^{5 represents} a radical of the formula (III)

# #

ONO stands, where

# denotes the link to the copolymer skeleton and

R ^{5 * has} the meaning given for R ⁵ .

In a preferred embodiment, R ^{2 is} C 1 -C 6 -alkyl, in particular C 1 -C 10 -alkyl, very particularly preferably C 1 -C ₄ -alkyl, such as methyl, ethyl, propyl or butyl, or hydrogen, especially methyl or hydrogen.

In a further preferred embodiment, R ^{3 is} hydrogen or C 1 -C 18 -alkyl, in particular C 1 -C 10 -alkyl, very particularly preferably methyl, ethyl, propyl or butyl, especially hydrogen or methyl.

In the self-organisates, therefore, the hydrophobic radical R ^{4 forms} the nonpolar tail, the radical R ⁵ (tetramethylpiperidinyl radical of the formula (II)) the polar head and L ¹ or the structural element C (O) -NC (O) is a polar linker.

The average number of repeat units is 3 to 100, preferably 3 to 30, in particular 5 to 12.

Preference is given to copolymers having a number-average molecular weight of from 1,500 to 10,000 daltons, in particular from 2,000 to 8,000 daltons, and more particularly from 2,500 to 6,000 daltons.

The copolymer is very particularly preferably an oligomeric compound of the formula (I.1)

)

wherein

R ^{4 is} C 16 -C ₃₂ alkyl; R ^{6 is} hydrogen, a Ci-Cβ-alkyl group or an O-radical (-O *), wherein at most 60 mol% of the radicals R ⁶ may be an O radical; and n is an integer from 5 to 15. The substituents R ⁴ and R ⁶ and the variable n independently of one another and preferably in combination have the following meanings:

n is preferably an integer from 5 to 12, in particular 5 to 10.

In a preferred embodiment R ⁴ in formula (1.1) a linear Ci6- C32 alkyl group, preferably a linear Ci6-C22-alkyl radical, more preferably Ci6-C ₂ o alkyl, _Ci7-C22 alkyl, Ci ₈ -C ₂ 2-alkyl, Ci _Θ -C ₂ 2-alkyl, C ₂ oC ₂ 2-alkyl or C ₂ iC ₂ 2-alkyl.

Equally preferably, R ⁴ in formula (1.1) is a branched C 16 -C 32 -alkyl radical. Suitable branched C 16 -C 32 -alkyl radicals are, for example, long-chain sec. Alkyl radicals of the formula (IV)

wherein q is O, 1, 2, 3 or 4;

R ⁸ and R ⁹ independently of one another represent linear alkyl,

with the proviso that the alkyl radical of the formula (IV) has 16 to 32 carbon atoms. Specifically, R ⁴ in formula (1.1) is a branched Ci7-C32-alkyl radical.

Alkyl radicals of the formula (IV) include those in which q is 0, such as. For example, 1-octyloctyl, 1-octylnonyl, 1-nonyldecyl, 1-decylundecyl, 1-nonylundecyl, 1-octylundecyl, 1-heptylundecyl, 1-undecyldodecyl, 1-decyldodecyl, 1-nonyldodecyl, 1-octyldodecyl, 1-heptyldodecyl , 1-hexyldodecyl, 1-pentyldodecyl, 1-dodecyltridecyl, 1-undecyltridecyl, 1-decyltridecyl, 1-nonyltridecyl, 1-octyltridecyl, 1-heptyltridecyl, 1-hexyltridecyl, 1-pentyltridecyl, 1-butyltridecyl, 1-tridecyltetradecyl, 1 Undecyltetradecyl, 1-decyltetradecyl, 1-nonyltetradecyl, 1-octyltetradecyl, 1-heptyltetradecyl, 1-hexyltetradecyl, 1-pentyltetradecyl, 1-butyltetradecyl, 1-propyltetradecyl, 1-undecycloctadecyl, 1-decyloctadecyl, 1-nonyloctadecyl, 1-octyllocatedecyl , 1-heptyloctadecyl, 1-hexyloctadecyl, 1-pentyloctadecyl, 1-butyloctadecyl, 1-propyloctadecyl, 1-ethyloctadecyl, 1-methyloctadecyl, 1-decyldocosanyl, 1-nonyldocosanyl, 1-octyldocosanyl, 1-heptyldocosanyl, 1-hexyldocosanyl, 1 Pentyldocosanyl, 1-butyldocosanyl, 1-propyldocosanyl, 1-ethyldocosanyl, 1-methyldocosanyl, and the like;

where q is 1, such as B .: 2-octyloctyl, 2-nonyldecyl, 2-octyldecyl, 2-heptyldecyl, 2-decylundecyl, 2-nonylundecyl, 2-octylundecyl, 2-heptylundecyl, 2-undecyldodecyl, 2-decyldodecyl, 2-nonyldodecyl, 2-octyldodecyl, 2 Heptyldodecyl, 2-hexyldodecyl, 2-pentyldodecyl and the like;

in which q stands for 2, such. B .:

3-octyloctyl, 3-nonyldecyl, 3-octyldecyl, 3-heptyldecyl, 3-decylundecyl, 3-nonylundecyl, 3-octylundecyl, 3-heptylundecyl, 3-undecyldodecyl, 3-decyldodecyl, 3-nonyldodecyl, 3-octyldodecyl, 3 Heptyldodecyl, 3-hexyldodecyl, 3-pentyldodecyl and the like:

where q is 3, such. For example: 4-octyloctyl, 4-nonyldecyl, 4-octyldecyl, 4-heptyldecyl, 4-decylundecyl,

4-nonylundecyl, 4-octylundecyl, 4-heptylundecyl, 4-undecyldodecyl, 4-decyldodecyl, 4-nonyldodecyl, 4-octyldodecyl, 4-heptyldodecyl, 4-hexyldodecyl, 4-pentyldodecyl and the like:

in which q stands for 4, such. B .:

5-octyloctyl, 5-nonyldecyl, 5-octyldecyl, 5-heptyldecyl, 5-decylundecyl, 5-nonylundecyl, 5-octylundecyl, 5-heptylundecyl, 5-undecyldodecyl, 5-decyldodecyl, 5-nonyldodecyl, 5-octyldodecyl, 5- Heptyldodecyl, 5-hexyldodecyl, 5-pentyldodecyl and the like:

Equally preferably, R ⁴ in formula (1.1) is a branched alkyl radical of the formula (V)

CH ₃

^CH 3 ² wherein m is 5, 6, 7 or 8, preferably 5 or 6.

In a further embodiment, R ^{4 is} a mixture of C 16 -C 32 -alkyl groups, especially C 1 -C 32 -alkyl groups, in particular C 18 -C 22 -alkyl groups, where two of these alkyl groups, which may not differ by more than two C atoms, in each case make up at least 30% of this mixture. In one embodiment, R ^{4 is} preferably linear alkyl groups. In a further embodiment, R ^{4 is} preferably branched alkyl groups. The presence of a mixture of alkyl groups for R ⁴ should be understood to mean, statistically, over the total Number of all copolymer molecules present two specific alkyl groups, which may not differ by more than two carbon atoms, each at least 30%, preferably each make up at least 40% of this mixture. In particular, these are mixtures of 3 specific alkyl groups, for. Octadecyl, icosayl and docoxyl, where two of these groups differing by 2 C atoms constitute more than 40% and the third group comprise 3 to 18% of the mixture; In this case, further alkyl groups with slightly more than 22 carbon atoms in slight amounts, usually less than 2%, may be present in the mixture.

In a preferred embodiment, R ⁶ in formula (1.1) is hydrogen or C 1 -C ₄ -alkyl. R ⁶ particularly preferably represents hydrogen or C ¹ -C 2 -alkyl, especially hydrogen or methyl.

In a very particularly preferred embodiment, in the formula (1.1), the substituents R ⁴ and R ⁶ and the variable n, independently of one another and preferably in combination, have the following meanings in particular:

n 5 to 10;

R ^{4 is} linear or branched C 16 -C 22 -alkyl; and R ^{6 is} hydrogen or methyl.

In a further particularly preferred embodiment of the invention, the copolymer of the formula (1.1) is an oligomer in which R ^{4 is} linear Cis-C22-alkyl and R ^{6 is} hydrogen. This oligomer is commercially available under the name Uvinul® 5050H from BASF SE.

In a further particularly preferred embodiment of the invention, the copolymer of the formula (1.1) is an oligomer in which R ^{4 is} linear Cis-C22-alkyl and R ^{6 is} methyl. This compound is also referred to as methylated Uvinul® 5050.

Copolymers of the formula (I) in which R ^{1 is} hydrogen and L ^{1 is} -C (O) -O- can be prepared by copolymerization of an alpha-olefin of the formula VI

in which R ^{4 has} the abovementioned meanings, with esters of the formula (VII)

wherein R ² , R ³ and R ^{5 have} the meanings given above, for example, based on Houben-Weyl, Methods of Organic Chemistry, Volume E20 / 2, p 1237-1248 (1987) are produced.

Alternatively, copolymers of the formula (I) in which R ^{1 is} hydrogen, L ^{1 is} -C (= O) O- and R ² , R ³ and R ^{4 have} the abovementioned meanings, can be prepared by copolymerization of the corresponding alpha-olefin of formula VI with a corresponding C ₁ -C ₆ -alkyl ester of 2-propenoic acid and subsequent transesterification with 2,2,6,6-tetramethylpiperidin-4-ol or 1 - (C ₁ -C ₆ -alkyl) -2,2, 6,6-tetramethylpiperidin-4-ol produce. This is a conventional transesterification, which can be carried out at elevated temperature, without solvent or in the presence of a solvent. It may be advantageous to carry out the reaction in the presence of a transesterification catalyst, for. As an acid or a base to perform.

Copolymers of the formula (I) in which R ^{1 is} hydrogen, L ^{1 is} -O-C (O) - and R ² , R ³ and R ^{4 have} the meanings given above, can be prepared by copolymerization of the corresponding alpha-olefin of the formula VI with the corresponding ester of the formula (VIII)

wherein R ² , R ³ and R ^{6 have} the meanings given above, are prepared.

Copolymers of the formula (I) in which R ^{1 is} hydrogen and L ^{1 is} -O- and R ² , R ³ and R ^{4 have} the meanings given above can be prepared by copolymerization of an alpha-olefin of the formula VI with the corresponding ether of Formula (IX)

wherein R ² , R ³ and R ^{6 have} the meanings given above, are prepared.

Copolymers of the formula (I) in which R ^{1 is} hydrogen, L ^{1 is} -C (= O) NR ⁷ - (in which R ^{7 has} the abovementioned meanings), and R ² , R ³ and R ^{4 have} the meanings given above , can be prepared by copolymerization of the corresponding alpha-olefins of the formula VI with corresponding propenoic acid esters, for example on the basis of Houben-Weyl, Methods of Organic Chemistry, Volume E20 / 2, pages 1237-1248 (1987) and subsequent reaction with the Aminotetramethyl compound of the formula (X) in which R ⁶ and R ^{7 have} the meanings given above,

getting produced.

Copolymers containing repeating units of the formula I in which R ^{6 is} C 1 -C ⁶ -alkyl can also be used, for example, by way of example. Example, by polymer-analogous alkylation with conventional alkylating agents starting from copolymers containing repeat units of the formula I, wherein R ^{6 is} hydrogen, are prepared.

Copolymers of the formula (I) in which R ¹ together with R ^{5 is} a radical of the formula (III) can be prepared by reacting maleic anhydride-α-olefin copolymers comprising repeating units of the formula (XI)

wherein R ^{4 has} the abovementioned meaning, with 4-aminotetramethylpiperidines of the formula (X), wherein R ^{7 is} hydrogen. The molar ratio of anhydride groups in (XI) to primary amine (X) is expediently 1: 1 or approximately 1: 1. Such reactions can be carried out in analogy to WO 94/12544.

Particularly suitable organic solvents are aromatic hydrocarbons such as toluene, xylene or mesitylene and halogenated or nitrohydrocarbons such as chlorobenzene, dichlorobenzenes or nitrobenzene. In particular, technical mixtures of such aromatics are important. In addition, however, aromatic-free hydrocarbon mixtures can also be used if they have a correspondingly high boiling range.

The reaction temperature should preferably be in the range from 120 to 200 ^° C., in particular from 140 to 175 ^° C. The water formed in the reaction is expediently distilled off azeotropically. The reaction is usually carried out at atmospheric pressure and is usually complete after 1 to 5 hours.

The maleic anhydride-alpha-olefin copolymers having structural units (XI) used as starting material are obtainable by known preparation processes by polymerization of maleic anhydride with the corresponding α-olefin of the formula VI, for example in analogy to Houben-Weyl, Methoden der Organi sche Chemie, Vol. E20 / 2, pp. 1237-1248 (1987).

The compounds of the formula VI, VII, VIII, IX and X are known from the literature or can be prepared by standard methods of organic chemistry.

In a further particularly preferred embodiment, the amphiphilic additive ii) is a light stabilizer which is a monomeric compound of the formula (XII)

wherein

R ^{5 is} a tetramethylpiperidinyl radical of formula II;

in which

R ^{6 is} hydrogen, C 1 -C ⁶ -alkyl or an O-radical (-O), wherein at most

60 mol% of R ⁶ may be an O radical; R ^{10 is} hydrogen; R ¹¹ -C ₃ 2-alkyl, hydrogen or C _6; R ¹² -C ₃ 2-alkyl, hydrogen or C _6; R ¹³ -C ₃ 2-alkyl, hydrogen or C _6; R ¹⁴ is Ci6-C ₃₂ alkyl or C ₆ -C ₃₂ - alkyl-C (= O); and X is O or NH;

or

R ¹⁰ together with XR ^{5 represents} a radical of the formula (XIII)

stands, where

# denotes the linkage with the carbon atom which carries the radicals R ¹¹ and R ¹² ,

* denotes the linkage with the carbonyl carbon atom; and R ^{5 * has} the meaning given for R ⁵ .

In a further preferred embodiment, the monomeric light stabilizer of the formula (XII) is a compound of the formula (XII.1) )

wherein

R11 is hydrogen or Ci6-C32-alkyl; R 12 is hydrogen or C 16-32 alkyl; R 13 is hydrogen or C 16-32 alkyl; R14 for Ci6-C ₃ is 2-alkyl; and

R ^{6 is} hydrogen, a Ci-Cβ-alkyl group or an O-radical (-O), wherein at most 60 mol% of the radicals R ⁶ may be an O-radical.

In a further preferred embodiment, the monomeric light stabilizer of the formula (XII) is a compound of the formula (XII.2)

wherein

X is O or NH;

R 10 is hydrogen; R11 is hydrogen or Ci6-C32-alkyl;

R ¹² -C ₃ 2-alkyl, hydrogen or C _6;

R ¹³ -C ₃ 2-alkyl, hydrogen or C _6;

R ¹⁴ is Ci6-C ₃₂ alkyl or C ₆ -C ₃₂ - alkyl-C (= O);

R ^{6 is} hydrogen, a Ci-Cβ-alkyl group or an O-radical (-0 *), wherein at most 60 mol% of the radicals R ⁶ may be an O-radical.

The monomeric light stabilizer of the formula (XII.1) can be prepared, for example, by reacting an appropriately substituted maleic anhydride (XVI)

wherein R ¹¹ , R ¹² , R ¹³ and R ^{14 have} the meanings given above, with 4-aminotetramethylpiperidines of the formula (X), wherein R ^{7 is} hydrogen, produce. The molar ratio of anhydride groups in (XVI) to primary amine (X) is expediently 1: 1 or approximately 1: 1. Such reactions can be carried out in analogy to WO 94/12544. Maleic anhydride of the formula (XVI) is commercially available or can be prepared according to standard methods of organic chemistry.

The monomeric light stabilizer of the formula (XI 1.2) in which X is O can be prepared, for example, according to standard methods of organic chemistry by transesterification of the corresponding C 1 -C 6 -alkyl esters of the formula (XVII)

in which R ¹¹ , R ¹² , R ¹³ and R ^{14 have} the abovementioned meanings and R "is C 1 -C 6 -alkyl, with 2,2,6,6-tetramethylpiperidin-4-ol or 1- (C 1 -C 6 -alkyl) Alkyl) - 2,2,6,6-tetramethylpiperidin-4-ol.

The monomeric light stabilizer of the formula (XII.2) in which X is NH may be prepared, for example, according to standard methods of organic chemistry by reacting the corresponding C 1 -C 6 -alkyl esters of the formula (XVII)

wherein R ¹¹ , R ¹² , R ¹³ and R ^{14 have} the meanings given above and R "is C 1 -C 6 -alkyl, with 4-aminotetramethylpiperidines of the formula (X) wherein R ^{7 is} hydrogen.

Esters of formula XVII are commercially available or may be prepared by standard organic chemistry methods.

The polymer composition according to the invention is a disperse system. The polyolefin is contained in the continuous phase and the at least one amphiphilic additive ii) is at least partially in the form of a continuous phase of self-organics having an average particle diameter of less than 200 nm. Specifically, the at least one amphiphilic additive ii) is at least partially dispersed in the continuous phase in the form of self-organizates having an average particle diameter of less than 100 nm.

Structural characterization of the amphiphilic additive ii) is particularly suitable for static and dynamic light scattering. Static and dynamic light scattering are methods known to those skilled in the art for characterizing disperse particles.

With dynamic light scattering (DLS), the size distribution of particles in liquids can be determined. The method exploits the scattering of laser light through the particles. Mathematical operations can be used to derive a particle distribution from the fluctuation pattern of the mean constant light scattering signal. To calculate the hydrodynamic diameter, ultimately only the viscosity of the dispersing medium and the temperature must be known. Since in this method the particle diameter is determined in solution, but the polymer composition according to the invention is solid at room temperature, it requires a polyolefin material which is liquid at room temperature. A suitable polyolefin substitute is squalane (2,6,10,15,19,23-hexamethyl tetracosane), an acyclic triterpene hydrocarbon. It is generally accepted that reliable predictions about the behavior of an additive in polyolefin can be made by the corresponding measurements in squalane.

The average diameter of the Selbstorganisats used in the invention (multi-mers) as determined by dynamic light scattering in squalane (c = 10 g / l) at 23 ⁰ C using an Autosizer Fa. Malvern Instruments, England, was typically in the range of 5 to 200 nm, preferably in the range of 5 to 100 nm, in particular in the range of 10 to 50 nm and especially in the range of 10 to 30 nm. The amphiphilic additive ii) used according to the invention can thus be distributed very homogeneously in the polyolefin composition.

Molecularly dissolved amphiphilic additives scatter the light in the same way as the continuous phase and are therefore not detected by the DLS.

The proportion of high molecular weight aggregates of amphiphilic additive ii) used according to the invention is very low and is typically below 5% at 23 ^° C. The aggregates are in equilibrium with the self-organizates. For example, if the aggregates are removed by filtration, the equilibrium between the aggregate and the self-assembly is restored. The calculated mean distance between the semicultures used according to the invention is at an application-technological concentration of 1% by weight in the nm range, for example in a range from 20 to 800 nm, preferably 40 to 200 nm, particularly preferably 50 to 100 nm.

In the polymer composition according to the invention, the amphiphilic additive ii) used according to the invention is in an application-typical concentration of 0.5 wt .-% to more than 65%, preferably more than 70%, in particular more than 75%, especially 79%, in the form of self-organics before and at a typical application concentration of 1 wt .-% to more than 75%, preferably more than 80%, in particular more than 85%, especially 89.5% in the form of self-organics before. The remaining portion of amphiphile is molecularly dissolved and / or in the form of aggregates, the proportion of aggregates is less than 5%.

Surprisingly, the average particle diameter of the self-organizate according to the invention is very small compared to other HAS compounds with an amphiphilic character and is in the nm range. Own investigations have shown that other HAS compounds having amphiphilic character, however, form aggregates having an average particle diameter in the micron range, aeration is true by DLS in squalane (c = 10 g / l) at 23 ⁰ C using an Autosizer the Messrs. Maenn Instruments, England. Accordingly, the calculated distance between these HAS units is in the μm range. At an application-technical concentration of 0.5 or 1% by weight, more than 70% of this HAS compound is typically present in the form of aggregates, for example at an application concentration of 0.5 or 1% by weight Chimassorb 944 has a proportion of 76% and 88% by weight, respectively, in the form of aggregates in the polymer composition.

It is known that HAS compounds and their oxidation products, such as. As hydroxylxylamine be deactivated by protonation of Piperidinylaminofunktion. It is believed that the ammonium salts thus formed no longer act as radical scavengers and the stabilization cycle is interrupted. The inventive polyolefin composition is surprisingly stable to acid. Even in the presence of 100 mol% conc. Sulfuric acid (based on the NH function (Piperidinylaminofunktion)) is still after 4 h, a part of the SeIb storganisate used according to the invention before. This could in squalane means of DLS (c = 10 g / l), will be confirmed at 23 ⁰ C using an Autosizer Fa. Malvern Instruments, England.

It is assumed that the surprising stability of the amphiphilic additive used according to the invention in relation to acid is due to the presence of self-organisates. In the self-organisates, the piperidinyl amino function is inside. The nonpolar tail group shields the amino function from attack by the acid. In addition, the surface of the self-assembly is polar tail group hydrophobic and shields the polar head group from the attack of the polar hydronium ion. Upon addition of acid, the piperidinylaminofunction of the unimers is protonated, with some of the protonated amphiphilic additive precipitating. This disturbs the equilibrium between unimers and self-organizers (multimers) and sets a new equilibrium.

In HAS compounds that form aggregates, the piperidinyl amino function is on the surface of the aggregates. They can therefore be easily protonated, disabling the HAS connection. In comparison with the amphiphilic additive used according to the invention, these HAS aggregates are deactivated more rapidly in the presence of acid.

In contrast to dynamic light scattering, static light scattering (SLS) does not consider the temporal fluctuations of the scattered light but the average of the scattering intensity. The absolute scattering intensity is proportional to the molecular weight of the molecule or the particle which consists of several molecules. The measured scattering intensity usually results from the interference of several particles. The determination of molecular parameters by means of SLS, however, is only possible with solutions. The average total molar mass of the amphiphilic additive ii) according to the invention in the form of self-organisates is from 15,000 to 100,000 daltons, preferably from 30,000 to 80,000 daltons and in particular from 40,000 to 70,000 daltons, determined by static light scattering in squalane. The oligomeric compound of formula 1.1, wherein R ^{6 is} hydrogen and R ^{4 is} Ci8-C22-alkyl, for example, has a mean total molecular weight of 59,000 daltons. This corresponds to about 108 unimers, or if one has an average molecular weight of 4500-5000 g / mol for the oligomeric

Compound of formula 1.1 starts, about 12-13 oligomeric compounds of formula 1.1

The polymer composition of the invention comprises at least one polyolefin as the continuous phase. In the context of the present invention, the term "polyolefin" encompasses all polymers which are built up from 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 monoolefins or diolefins.

Ethylene polymers:

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

- ULD (ultra low density) ULD, very low density VLD (VLD); Copolymers and terpolymers of ethylene with up to 10% of octene, 4-methylpentene-1 and because 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 ⁰ C with oxygen or peroxides as catalysts in autoclaves or tubular reactors. Highly branched with branches of different lengths, crystallinity 40 to 50%, density 0.915 to 0.935 g / cm ³ , average molecular weight to 600 000 g / mol.

- LL-LLD (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 copolymeric PE-LLD.

PE-HD (HD = High Density), available according to the medium pressure (Phillips) and low pressure (Ziegler) method. After Phillips at 30 to 40 bar, 85 to 180 ⁰ C,

Chromium oxide as catalyst, molecular weights about 50 000 g / mol. After Ziegler at 1 to 50 bar, 20 to 150 ⁰ 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. B. Lupolene® (Basell, The Netherlands).

Especially preferred is polyethylene produced using metallocene catalysts. Such polyethylene is z. B. as Luflexen® (Basell, Netherlands) commercially available. As ethylene copolymers, all commercially available ethylene copolymers are suitable, for example Luflexen® types (Basell, Netherlands), Nordel® and Engage® (DuPont-Dow, USA). As comonomers z. B. α-olefins having 3 to 10 carbon atoms, in particular propylene, but-1-ene, hex-1-ene and oct-1-ene, also alkyl acrylates and methacrylates having 1 to 20 carbon atoms in the alkyl radical, especially butyl acrylate. Other suitable comonomers are dienes such as. Butadiene, isoprene and octadiene. Further suitable comonomers are cycloolefins, such as cyclopentene, norbornene and dicyclopentadiene.

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.

HDPE mainly manufactures toys, household items, technical hardware and beer crates. Some types of HDPE are used in disposables and mass-produced articles of daily use. The field of application of LDPE extends from films over paper coating to thick and thin-walled molded parts. LLDPE shows advantages over LDPE in terms of mechanical properties and stress cracking resistance. Application of LLDPE is mainly found in pipes and 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 which can be copolymerized with propylene, for example C 2 -C 5 -alk-1-enes, such as. a. Ethylene, but-1-ene, pent-1-ene or hex-1-ene. Two or more different comonomers can also be used.

Suitable polypropylenes include 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 here 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-enes with up to 8 C -Atomen 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 hinzupo - lymerised. 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 also 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 8 -alk-1-enes can be used. Suitable reactors are u. a. 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 ⁰ C, in particular from 50 to 100 ⁰ 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 ⁰ C and under a weight of 2.16 kg, up. In a further embodiment of the invention, the polyolefin comprises, in copolymerized form, at least one monomer which is selected from ethylene, propylene, but-1-ene, isobutylene, 4-methyl-1-pentene, butadiene, isoprene and mixtures thereof. Suitable homopolymers, copolymers of said olefin monomers and copolymers of at least one of said olefins as the main monomer and other monomers (such as vinyl aromatic) as comonomers.

Preferred polyolefins are low density polyethylene homopolymers (PE-LD) 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 (eg PP / HDPE, PP / LDPE) and blends of different types of polyethylene (eg LDPE / HDPE).

Another embodiment of the present invention relates to a composition wherein the polyolefin is selected from copolymers of mono- or di-olefins with vinyl monomers and mixtures thereof. These include ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and blends thereof with low density polyethylene (LDPE), propylene / but-1-ene copolymers, propylene / isobutylene copolymers, ethylene / but-1-ene copolymers , Ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, Ethylene / vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethylidene norbornene and polyolefin blends with elastomer components such as EDPM (so-called thermoplastic polyolefins); and mixtures of such copolymers with each other and with the above-mentioned polymers, e.g. Polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA, and alternating or random polyalkylene / carbon monoxide copolymers and blends thereof with other polymers, e.g. B. polyamides.

In a further embodiment, the polymer composition according to the invention additionally contains at least one further additive other than the amphiphilic additive ii). The additive other than the amphiphilic additive ii) may be selected from light stabilizers and other (co) stabilizers. Of course, the additionally used light stabilizer and optionally used (co) stabilizers must (must) be compatible with the amphiphilic additive ii). Preferably, they are colorless in the visible range or have only a slight intrinsic color. Preferably, the optionally used sunscreen agents have tel or (co) stabilizers on a high migration stability and temperature resistance. Suitable light stabilizers and other (co) stabilizers are selected, for example, from groups a) to s):

a) 4; 4-diarylbutadienes; b) cinnamic acid ester; c) benzotriazoles; d) hydroxybenzophenones; e) diphenylcyanoacrylates; f) oxamides (oxalic acid diamides); g) 2-phenyl-1,3,5-triazines; h) antioxidants; i) nickel compounds j) other sterically hindered amines; k) metal deactivators;

I) phosphites and phosphonites; m) hydroxylamines; n) nitrones; o) amine oxides; p) benzofuranones and indolinones; q) thiosynergists; r) peroxide-destroying compounds; and 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 R 1 and / or R n are preferably C 1 -C 8 -alkyl and C 5 -C 8 -cycloalkyl.

The group b) of the cinnamic acid esters includes, for example, 4-methoxycinnamic acid isoamyl ester, 4-methoxycinnamic acid 2-ethylhexyl ester, 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-triazole) 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-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chloro-benzo triazole, 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'-benzotriazole) 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 ) S] ₂ , with R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl 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 SE, Ludwigshafen, 2-ethylhexyl-2-cyano-3, 3-diphenylacrylate, which is commercially available for example as Uvinul® 3039 Fa. BASF SE, 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 commercially available, for example, under the name Uvinul® 3030 from BASF SE, Ludwigshafen.

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

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-butyloxy-propoxy) -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-3 - dodecyloxy-propoxy) phenyl] -4,6-bis (2,4-dimethylphe nyl) -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, 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-butylphenol 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 branched-chain nonylphenols such as, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1-methyl und 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-didodecylthiomethyl-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, for example, 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) disulphide.

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'-methylenebis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylene bis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidene bis (4,6-di-tert -butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol],

2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylene bis (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-dodecylmercaptobutan,

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-hydroxy-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 octadecyl 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-methyl- benzyl) 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-hydroxy) phenoxy) -1, 3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1, 3,5-triazine, 1, 3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6 Tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

h.11) benzyl phosphonates such as, for example, dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate

((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 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, neo pentyl 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.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) oxamide,

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. N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexamethylenediamine, N, 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 Uniroyal).

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-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- ( 4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p, p'-di-tert-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, mixture of mono- and dialkylated tert-butyl / tert-Octyldiphenyl- amines, mixture of mono- and dialkylated nonyldiphenylamines, mixture of mono- and dialkylated dodecyldiphenylamines, mixture of mono- and dialkylated isopropyl / isohexyl-diphenylamines, mixture of mono- and dialkylated tert-butyldiphenylamines, 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-octyl-phenothiazines,

N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperidin-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, polymer based on 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-dispiro [5.1.11.2] -heicosan-21-one and epichlorohydrin [CAS No .:

202483-55-4], (for example Hostavin® N30 from Clariant, Germany.), Compounds which contain repeating units of the formula (XIV),

wherein n is an integer from 1 to 100, for example 2 to 20, preferably 3 to 50, for example 5 to 15, in particular 8 to 14,

z. Example, the dimethyl succinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol [CAS number 65447-77-0], (for example, Tinuvin® 622 Fa. Specialty Chemicals, Inc. , Chisorb® 622 or Lowilite® 622), or a 2,2,6,6-tetramethylpiperidine compound of the formula (XV)

wherein

X is O or NH;

R ^{15 is} C 16- C ₃ 2-alkyl; and R ^{16 is} hydrogen, a Ci-Cβ-alkyl group or an O-radical (-0 *), wherein less than 30 mol% of the radicals R ¹⁶ may be an O-radical.

Compounds of the formula (XV) in which R ^{16 is} hydrogen and R ^{15 is} predominantly C 1 -C 18 -alkyl are commercially available, for example, under the name Cyasorb 3853, Cytec.

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-butylbenzylphosphonic acid monoalkyl esters such as e.g. As the methyl or ethyl ester, nickel complexes of ketoximes such. Example of 2-hydroxy-4-methylphenylundecyl ketoxime, nickel complex of 1-phenyl-4-lauroyl-5-hydroxypyrazole, optionally with additional ligands.

The group j) of the further 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-2,2,6,6-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, 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-tetracarbo xylate, 1,1 '- (1,2-ethanediyl) -bis (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- 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 SE, 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, 2, 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 -dodec yl-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. [136504-96-6]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1, 2,2,6,6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 2-undecyl 7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro [4,5] decane, reaction 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-methoxymethylene 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, 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-tetramethylpi peridine 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) -4-oxo-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) -2,6,6,6-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 [1- (2-hydroxy-2-methylpropoxy) -2 , 2,6,6-tetramethylpiperidin-4-yl] -N-butylamino} -6- (2-hydroxyethylamino) -s-triazine, 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] fluoren-4,8-dione (e.g. Uvinul® 4049 from BASF SE, 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], 1, 3,5-triazine-2,4,6-triamine, N, N ', N ", N'" - tetrakis (4,6-di (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. B. Chimassorb 1 19 from Ciba Specialty Chemicals, Inc.).

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 acid dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide.

The group I) of the phosphites and phosphonites includes, 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, diisodecylpentaerythritol diphosphite, bis (2,4-di-tert-butyl -6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol tri- phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite , 6-isoctyloxy-2,4,8,10-tetra-tert-butyl-dibenzo [d, f] [1,2,2] dioxaphosphepin, 6-fluoro-2,4,8,10-tetra-tert-butyl- butyl 12-methyldibenz [d, g] [1,2,2] 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-t tert-butyl-1, 1'-biphenyl-2,2'-diyl) phosphite], 2- (ethylhexyl) - (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl -2,2'-diyl) phosphite.

The group m) of the hydroxylamines include, for example, N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, 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-heptadecyl nitrone,

N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecyl nitrone, N-heptadecyl-α-heptadecyl nitrone, N-octadecyl-α-hexadecylnitrone, N-methyl-α-heptadecyl nitrone, and nitrenes derived from N, N-dialkylhydroxylamines from hydrogenated tallow fatty amines. The group o) of the amine oxides includes, for example, amine oxide derivatives as described in US Patent 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 includes, for example, those described in U.S. Patents 4,325,863; 4,338,244; 5,175,312; 5,216,052; 5,252,643; in DE-A-4316611; in DE-A-4316622; in DE-A-4316876; or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2 (3H) -one, 5.7, described in EP-A-0589839 or EP-A-0591102 -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- butyl-benzofuran-2 (3H) -one, 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-butylbenzofuran (3H) 2-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 the basic costabilizers include, for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, metal salts of saturated or unsaturated carboxylic acids having 7 to 30 carbon atoms, antimony catecholate or zinc catecholate.

In a particularly preferred embodiment of the invention, the light stabilizer other than the amphiphilic additive ii) is selected from amine-containing antioxidants of group h.19). The ratio of amphiphilic additive ii) and the amine antioxidant group h.19) is usually 99 to 30 wt .-%, preferably 99 to 50.0 wt .-%, in particular 99 to 50.1 wt .-% amphiphilic Additive ii) and 1 to 70 wt .-%, preferably 1 to 50.0 wt .-%, in particular 1 to 49.9 wt .-% of amine antioxidant group h.19). Of these, particular preference is given to those aminic antioxidants which are selected from the compounds having repeating units of the formula (XIV) and compounds of the formula (XV). Preferred amine antioxidants of group h.19) are, for example, compounds as commercially marketed under the name Tinuvin® 622, Ciba Specialty, and Cyasorb 3853, Cytec.

In a preferred embodiment, the polymer composition according to the invention additionally contains at least one metal salt of a saturated or unsaturated fatty acid having 12 to 30 carbon atoms, wherein the metal is selected from alkali metals or alkaline earth metals or a transition metal of the 1 1 or 12 group. Preferred salts are e.g. Stearates, laurates, palmitates, behenates, ricinolates and hydroxystearates. Particular preference is given to behenates, stearates, palmitates and mixtures thereof, for example calcium stearate, magnesium stearate, copper stearate,

Zinc stearate, magnesium behenate, calcium behenate, potassium palmitate or mixtures thereof. Very particular preference is given to calcium stearate, magnesium stearate and zinc stearate, as well as calcium behenate and zinc behenate.

Furthermore, the polymer composition according to the invention may contain further additives and additives. In a further embodiment, the polymer composition according to the invention additionally contains at least one further additive or further additive, selected from nucleating agents, fillers or reinforcing agents, antistatic agents, colorants, lubricants, flameproofing agents, biocides and pigment distributors.

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 car- Bonsäureester- 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 may be an inorganic or organic 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 green, 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, Indanthronpigmen- te, Indolinonpigmente, isoindoline pigments, isoindolinone pigments, thioindigo pigments, metal complex pigments, Perinone pigments, perylene pigments, pyranthrone pigments, phthalocyanine pigments, thioindigo pigments, triarylcarbonium pigments or metal complex pigments.

Suitable organic pigments include: Examples of organic pigments are: Cl. (Color Index) 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 170, 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 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.

Suitable pigment distributors include i.a. Polyacrylic acids or copolymers of acrylic acid, methacrylic acid, maleic anhydride, itaconic acid, fumaric acid or

Crotonic acid with comonomers such as (meth) acrylic esters, styrene, alpha-olefins, maleic monoesters and long-chain vinyl esters of Versatic acids. Furthermore, as pigment distributors and polyphosphates, u.a. Sodium or potassium polyphosphates are used, for example, Densodrin BA® BASF SE, a copolymer of maleic anhydride with a Ci6-C2o-alpha-olefin, wherein the anhydride groups were opened with NaOH to the disodium salt or Collacral ® LR 8954 the company BASF SE in the form of a copolymer of acrylic acid and n-butyl acrylate, which is neutralized with ammonia.

The powdered fillers, including the pigments, may be surface pretreated. You can e.g. have been made more compatible with the polymer melt by impregnation with an adhesion promoter, or be pretreated so that, for example, the flowability of the powdered fillers and / or their distribution in a polymer melt is improved.

The amphiphilic additive ii) used according to the invention can be added to the material to be stabilized in customary amounts, generally in a concentration of 0.01 to 5% by weight. It is preferable to add amphiphilic additive ii) 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 polymer composition to be stabilized. The total weight of the polymer composition is understood as meaning the weight of the staggered with the amphiphilic additive ii) and optionally further (co) stabilizers Polymer composition (polymer + 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 polymer composition.

The content of colorant in the polymer composition according to the invention depends on the color requirement which the product produced from the composition according to the invention is to have and can therefore vary widely. If present, the colorant component in an amount of 0.0001 to 10 wt .-%, preferably 0.001 to 5 wt .-%, particularly preferably 0.01 to 3 wt .-% and most preferably 0.1 to 2 wt .-%, based on the total weight of the inventive polymer composition used.

The additives selected from nucleating agents, fillers or reinforcing agents, antistatic agents, colorants, lubricants, flame retardants, biocides and pigment dispersants 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 polymer composition.

The present invention also provides a process for the preparation of the polymer composition, wherein a polyolefin is plasticized and in the plasticized state with the amphiphilic additive ii) brings into intimate contact.

The plasticizing takes place in a plasticizing unit. For this, energy must be supplied to the material. This energy is supplied by heat output of cylinder and screws as well as by friction and shear. The intimate contact is preferably carried out with the input of shear energy.

Here, the polyolefin component is heated above its specific melting temperature, so that a homogeneous polymer composition is formed. The plasticizing preferably takes place in an extruder. In principle, conventional extruder types known to the person skilled in the art are suitable for the process according to the invention. These usually include a housing, a drive unit, a plasticizing unit of one or more provided with transport and / or kneading elements rotating axes (screws) and a control unit. Along the screw, several zones extend in the transport direction, which in the method according to the invention comprise a feed zone, a heating zone, a kneading zone and an ejection zone. Each zone may in turn comprise one or more cylinders as the smallest independent unit. Optionally, the extruder contains venting parts. Suitable extruders are single screw extruders, twin screw extruders and multi-screw extruders. In a preferred embodiment, a twin-screw extruder is used. Several screws can be made in the same direction or in opposite directions, rotating, combing or tightly combing. Preferably, it is a twin-screw extruder, which is particularly preferably in the same direction rotating and tightly combing.

In the heating zone of the extruder, the screw geometry can be chosen to be tight-meshing, combing or non-combing, with a tight-meshing screw geometry being preferred. The screws can rotate in opposite directions or preferably in the same direction. In the mixing area mixing elements and kneading elements are preferably arranged in addition to conveying elements on the screws. Conveying elements are single and multi-start screw elements of different pitch. Mixing elements are gear-toothed pulley elements or provided with openings backward-promoting elements, wherein the openings may extend partially to the screw core or make up at least half of the helical radius. Kneading elements are two- or dreppitzscheiben, the elements always have several discs with different width and different offset angle to each other.

The heating zone is followed by a kneading zone, in which the polyolefin component i) is melted. The kneading zone consists essentially of mixing and kneading elements and optionally of return elements.

If necessary, short conveying elements can also be installed between heating zone and kneading zone, just as it may be advisable to provide short conveying paths between the mixing elements or the kneading elements.

The detailed screw geometry also depends on the order in which the components are added and, in special cases, on the type of components used.

The ejection zone adjoining the kneading zone may comprise at least one device for further processing of the extrudates, such as, for example, B. have an injection molding machine, blow molding or crushing plant. For example, a conventional cutting granulator can be used to produce granules.

Optionally, it may be advantageous that the extruder contains at least one degassing zone. In the area of the degassing zone, the screw is then advantageously equipped with both conveying elements and kneading elements. In a first embodiment of the method according to the invention, the extruder is fed in a first feed zone with the polyolefin component i) and in a second feed zone with the amphiphilic additive ii). Of course, this supply can also be done in a common first intake zone. Furthermore, a premix of polyolefin component i) and amphiphilic additive ii) can be used to feed the extruder. If further additives and additives are used, they can be metered in together with the polyolefin component i) and / or the amphiphilic additive ii) in one or more further feed zones. The temperature in the first, second and, if present, further feed zones is usually below 50 ^° C. A suitable temperature range is e.g. B. 10 to 45 ⁰ C, for example 15 to 30 ⁰ C.

The dosed components are conveyed by means of the conveying elements of the screw into the heating zone of the extruder. A heating zone is connected to the intake zone (s). The temperature in the heating zone is usually in the range of 50 to 100 ⁰ C, especially 50 to 90 ⁰ C.

The extruder has a kneading zone downstream of the heating zone along the extruding device. In this kneading zone, the polyloefene component i), if necessary with heating, is melted and brought into intimate contact with the amphiphilic additive ii) and, if appropriate, further additives and additives, so that a total flowable mixture is formed. The mixture is usually at a melt temperature in the range of 120-300 ⁰ C, preferably 150 to 280 ⁰ C, in particular 170 to 250 ⁰ C promoted by the Knetzone to the ejector. Preferably, the homogenization effect of the screws is reinforced by appropriately designed mixing elements. In addition, the forced delivery can be interrupted in order to force a more intensive exchange of material.

The actual ejection device consists essentially of the extruder head or the connected ejection nozzle, -blende or other outlet opening, for. B. a round nozzle, slot die or pinhole. The temperature in the metering zone is preferably more than 150 ⁰ C, particularly preferably more than 155 ⁰ C and in particular about 160 ⁰ C.

In a further (second) embodiment of the method according to the invention, the extruder is fed in a feed zone with the polyolefin component i), conveyed by means of conveying elements into the heating zone and melted in a kneading zone characterized predominantly by mixing elements. Thereafter, the amphiphilic additive ii) and optionally further additives and additives are metered in together or in succession in any order and homogenized in a further mixing range with the polymer melt. Thereafter, the melt is supplied to the ejector. In a further (third) embodiment of the process according to the invention, the extruder is fed in a feed zone with the polyolefin component i), conveyed by means of conveying elements into the heating zone and melted in a kneading zone characterized predominantly by mixing elements. The amphiphilic additive ii) and optionally further additives and additives are metered together or successively in any order in the heating zone. Alternatively, they are added in the heating area and / or kneading area. With regard to the further procedure, reference is made to the above.

The polyolefin component can be added in the form of pellets, granules or powder. The amphiphilic additive ii) used according to the invention can be added in the form of granules, powder or in the form of pellets.

The amphiphilic additive ii) used according to the invention can also be used in the form of a premix (masterbatch). The masterbatch contains the amphiphilic additive ii), for example in a concentration of 1 to 60, preferably 2.5 to 30 wt .-%. Furthermore, the masterbatch may also contain any additives and additives that may be used.

At the ejection zone, at least one device for further processing of the extrudates, such. B. connect an injection molding machine, blow molding or crushing. For example, a conventional cutting granulator can be used to produce granules.

To carry out the process according to the invention, the screws of the extruder are preferably operated at a rotational speed in the range from 100 to 1500 rpm, preferably from 250 to 1000 rpm.

The residence time of the components i), ii) and optionally of the further additives and additives in the extruder depends inter alia on the degree of filling with which the extruder is operated.

The polymer composition obtained according to the invention at the extruder head or at the outlet opening is generally in the form of a continuous extrudate of preferably constant cross-section, e.g. B. in the form of a band or strand, in particular with a round, oval, rounded or flat and wide cross-section, and can be removed and further processed before or after solidification. Advantageously, at least one molding step subsequent to the outlet opening of the extruder takes place before complete solidification. After solidification, the resulting polymer composition according to the invention for further processing, in particular for further shaping, in a variety of Tools, in particular for injection molding or film extrusion, transferred. Alternatively, they can be transferred for this purpose before complete solidification in such a tool, for. B. be extruded directly.

The molding before solidification can be done by molding, injection molding, film extrusion, pressing, crushing or calendering. The polymer composition of the invention can be such. B. in granular form or directly obtained as a film.

Suitable shaping steps for extrudates following the self-shaping discharge opening of the extruder are, in particular, the cold cut, the hot break and the squeezing of the strand, which is not yet completely solidified, in a squeezing device, which is a conventional method known to the person skilled in the art. Cold cut means cutting or chopping the strand after at least partial solidification, hot cutting cutting or chopping the strand before its solidification. With hot or cold deduction in particular granules (hot or cold granulation) and pellets can be produced.

The polymer composition according to the invention, in particular in the form of granules, is particularly advantageous for use as feedstock in injection molding, rotational sintering ("slush molding") or film extrusion processes, especially for the production of moldings, fibers and films , in particular for the production of agricultural films.

The term "agricultural film" is understood in the context of the present invention, a plastic film, which is used outdoors in agriculture. Examples of agricultural films are films for round bales, silage films, early harvesting films, early bed tunnels, mulch films, nonwovens, greenhouse films, etc. Agricultural films offer, for example, weather protection and protection against pest infestation and grazing. Furthermore, the term "agricultural film" in the context of the present invention comprises polyolefin nets, which are used as an aid to bird control in agriculture.

A further subject of the present invention therefore relates to an agar film which contains or consists of the polymer composition according to the invention. Component i) preferably consists of polyethylene (PE) homo- and copolymers, polypropylene (PP) homo- or copolymers, such as PE-LD, PE-LLD or copolymers of ethylene and vinyl acetate or ethylene and butyl acrylate. Component ii) is preferably an oligomer of formula 1.1, wherein R ² , R ³ R ⁵ and n have the meanings given above, in particular the meanings mentioned as preferred.

The lifetime of agricultural films depends on many factors such as the material, the thickness, the stabilization of the film, etc, but also external influences like climate, acid rain and agrochemicals. The agrochemicals are, for example, sulfur- or halogen-containing compounds, ammonium compounds or compounds having carboxyl groups. Harmful sulfur compounds are z. As sulfur dioxide, which arises when burning sulfur, or can come from the air (acid rain) or hydrogen sulfide from fouling gases. Acid rain refers to precipitation whose pH value is lower than the pH value that arises in pure water due to the natural carbon dioxide content of the atmosphere (<pH = 5.5). Components of acid rain include sulfur oxides and nitrogen oxides. The sulfur oxides or nitrogen oxides form with sulfuric acid or nitric acid.

Another object of the present invention is a method of plant culture, wherein

(i) at least partially surrounds a crop with an agricultural foil according to the invention; and

(ii) the crop is treated once or several times with an agrochemical, the agrochemical or its microbial metabolite having a pKs

Value less than 15.74 at 25 ⁰ C.

The agricultural films of the invention are characterized by a high tolerance to acids and agrochemicals, wherein the agrochemical or its microbial metabolite a pKs value less than 15.74, z. B. in the range of -10 to 13, preferably -7 to 10, especially -7 to 7.2, at 25 ⁰ C. Agricultural films stabilized according to the invention have a significantly greater acid resistance compared to agricultural films of the prior art than agricultural films which contain structurally similar HAS compounds and therefore have a prolonged service life.

Another object of the present invention is the use of an agricultural film according to the invention in a plant culture, which comes into contact with compounds having an acidic character. The agricultural film according to the invention surprisingly has excellent stability against compounds having an acidic character.

The amphiphilic additive ii) used according to the invention can form self-organisates with a particle diameter of less than 200 nm, especially less than 100 nm, and can therefore be distributed very well in the polymer composition. The presence of self-organisates gives the polymer composition excellent properties, such as high protection against protonation. In addition, the polymer composition according to the invention shows little or no water carry over during production and good hot tack. Due to their aggregate formation, conventional HAS compounds can only be distributed insufficiently homogeneously in the polymer. Aggregate formation does not provide protection against protonation and has a negative impact on the water carrry over effect, on the heat seal and on base-sensitive pigments.

The following examples are intended to illustrate the invention without, however, limiting it. Unless otherwise stated, the percentages are by weight.

Examples

HAS connections used:

H1: Uvinul 5050 H, BASF SE, density: 0.99 g / cm ³ ± 5% at 20 ⁰ C,

= C ₁₈ -C ₂₂ alkyl

H2: methylated Uvinul® 5050 H, BASF SE

R = C ₁₈ -C ₂₂ -alkyl

H3:

R = C ₁₆ -C ₂₀ -alkyl

H4: mixture of Uvinul® 5050 (H1) and Tinuvin 622 (VH7) in the ratio 1: 1; H5: Mixture of Uvinul® 5050 (H1) and Tinuvin 622 (VH7) in the ratio 7: 3; H6: Mixture of Uvinul® 5050 (H1) and Tinuvin 622 (VH7) in the ratio 3: 7; H7: Mixture of Uvinul® 5050 (H1) and Tinuvin 622 (VH7) in the ratio 6: 4; H8: Mixture of Uvinul® 5050 (H 1) and Cyasorb 3853 (VH6) in the ratio 1: 1;

VH1: Chimassorb® 2020, Ciba Specialty

1, 6-hexanediamine, N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -polymer with 2,4,6-trichloro-1, 3,5-triazine, reaction products with N- Butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine; CAS: 192268-64-7

VH2: Chimassorb® 944, Ciba Specialty

Poly [[6 - [(1,1,3,3-tetramethylbutyl) amino] -s-triazine-2,4-diyl] [[(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino];

CAS: 70624-18-9

VH3: Chimassorb® 1 19, Ciba Specialty,

1, 3,5-triazine-2,4,6-triamine, N, N '"- [1,2-ethanediylbis [[[4,6-bis [butyl (1, 2,2,6,6-pentamethyl-

4-piperidinyl) amino] -1,3,5-triazin-2-yl] imino] -3,1-propanediyl]] - [N ', N "-dibutyl-N', N" - bis (1, 2,2,6,6-pentamethyl-4-piperidinyl); CAS: 106990-43-6 RR

I

R-NH- (CH ₂ ) ₃ -N- (CH _Z ) ₂ -N- (CH ₂ ) ₃ -NH-R

VH4: Cyasorb® 3346, Cytec, CAS: 082451-48-7;

VH5: Cyasorb® 3581, Cytec;

VH6: Cyasorb® 3853, Cytec, CAS: 167078-06-0

VH7: Tinuvin® 622, Ciba Specialty, CAS: 65447-77-0

VH8: Tinuvin® 783, blend of VH7 and VH2; CAS: 71878-19-8 + 65447-77-0

VH9: C ₁₂ alkyl

R _j alkyl

1. Critical micelle concentration (cmc)

1.1 Uvinul 5050, H1

The cmc in squalane is less than 1 g / I.

1.2 Chimassorb® 944, VH2

The cmc in squalane is less than 0.05 g / l.

2. Estimation of the proportion of self-organizates / agglomerates in application-typical concentrations

2.1 H1

A solution of H1 in squalane (c = 1 g / l, density of squalane: 0.81 g / cm ³ (20 ^° C.)) was filtered through a 20 nm filter and the concentration of the solution was determined by IR measurement and Comparison with a calibration line determined. The concentration of molecular Kular dissolved H1 was determined at a starting concentration of 1.25 g / 1000 g to 1.05 g / 1000 g. 16% of H1 are present in micelles at this concentration. If this result is transferred to an application-typical concentration of 0.5% or 1% stabilizer in the polymer, then 79% or 89.5% of the amount of stabilizer used is present in micelles.

2.2 VH2

A solution of VH2 in squalane (c = 1 g / l) was filtered through a 45 nm filter. The absorbance of the filtered sample was then compared to the reference at two bands. The average decrease was 4.2%. The vast majority of the sample was thus solved.

Assuming that the aggregates are also superstructures created by self-organization, then, at an application concentration of 0.5% or 1%, a proportion of stabilizer in large aggregates of 76% or 88% is calculated.

3. Determination of the hydrodynamic particle diameter.

A solution of H1 in squalane (c = 10 g / l) was heated at 90 ^° C. for 10 h. Subsequently, the clear solution was allowed to cool to room temperature and determined the average particle diameter by means of DLS at 23 ⁰ C.

In an analogous manner, solutions of H2, M-N-oxyl, VH1, VH2, VH3, VH4, VH5 and VH6 were prepared.

The determined hydrodynamic particle diameter as well as the calculated particle edge and the edge distance are summarized in Table 1. The measuring concentration was always 10 g / l. The measurement temperature was 23 ⁰ C.

Table 1 :

Calculation of the particle edge and the edge distance using the example of VH2:

Density LDPE: ~ 0.925 g / cm ³ at 20 ⁰ C Density VH2: ~ 1, 01 g / cm ³ at 20 ⁰ C

Assumption: density LPDE ~ density VH2

At an application concentration of 1% by weight of VH2, one particle of VH2 is obtained on 99 parts of LDPE. If one imagines this as a cube consisting of 100 particles or smaller cubes, then the edge length amounts to

Lwurfeikante = (100) ^1/3 = 4.64 particles

The diameter of a VH2 aggregate is 1, 2 μ. V = 4 / 3π ^» r ³ = 0.905 μ ³

If one converts the sphere volume into a cube, one obtains

Lτe, lchenkante = (0.905) ^1/3 = 0.97 μ

The length of the cube edge, which consists of 4.64 particles, is obtained as the edge distance between the VH2 particles

L edge distance = 0.97 ^• 4.64 μ = 4.5 μ

It can be seen that the amphiphilic additive used according to the invention in the presence of stearates is furthermore in the form of self-organisates with a particle diameter of less than 100 nm.

4. protonation

4.1 H1

To a solution of H1 in squalane (c = 10 g / l) was added in each case 10 mol%, 50 mol% and 100 mol% (based on NH) of conc. Sulfuric acid. An average molecular weight of 544 g / mol was assumed for the repeat unit in H1. The concentration of protonatable amine was thus 18.38 mmol / l. There were sulfuric acid concentrations of 0.18 g / l, 0.9 g / l and 1, 8 g / l. The samples were like dissolved at 90 ⁰ C and cooled to 23 ° C. Upon addition of H2SO4, the samples initially became cloudy, streaks formed. After 4 hours, the samples were sedimented and the supernatant clear. The samples were examined with DLS.

The addition of the acid initially disrupted the order. The protonation freed free stabilizer molecules from their equilibrium and released more molecules from the micelles. Part of the protonated HAS compound failed. However, particles with a diameter of 20 nm were still detectable.

4.2 VH2

To a solution of VH 2 in squalane (c = 10 g / l) was added in each case 10 mol%, 50 mol% and 100 mol% (based on NH) of conc. Sulfuric acid. The sulfuric acid concentrations were 0.18 g / l, 0.9 g / l and 1.8 g / l, respectively. The repeating unit of VH2 has a molecular weight of 430 g / mol and realistically possesses 7 protonatable amino functionalities. This corresponds to 61 g / mol per protonatable N and at 10 g / l VH2 a concentration of 163.9 mmol / L amine. The amine concentration is thus almost ten times as high as in H1. After adding the sulfuric acid, the squalane solution does not change optically, it remains slightly cloudy. In the measurement, even with the addition of 1.8 g / l sulfuric acid (which would correspond to about 10 mol% here), no significant change in the aggregates was recognized.

Since, due to the much higher density of polar amine functions, these must also be located on the surface of the aggregates, it can be expected that the piperidylamines contributing to the stabilization can be easily protonated and the aggregate formation, in contrast to micelle formation, has no protective function.

5. Comparison of pKs values of some HAS compounds

The pKs value is a measure of the acid strength and can be used to compare the acid resistance of the amines. Since it is defined for water in which some of the partially highly hydrophobic HAS compounds are not soluble, the measurement was carried out in a mixture of xylene / propanol / water, which allows a qualitative comparison.

The greater acid tolerance of H1 is reflected by an order of magnitude lower pKs. This is more on the order of methylated HAS compounds. Table 2 lists pKs values of some HAS compounds measured at 23 ^° C. For this purpose, about 0.1 g of sample was dissolved in 10 ml of xylene with 40 ml of 2-

Propanol diluted and then treated with 2 ml of water. The resulting solution was titrated with trifluoromethanesulfonic acid / 2-propanol. The resulting pKs value refers to this solvent mixture.

Table 2:

becomes cloudy during titration

6. Determination of the molar mass

The determination was carried out by SLS at 23 ⁰ C in squalane. In order to determine the molecular weight of the individual particles, the measurement was carried out at several angles and concentrations. The molecular weight was obtained by extrapolation to 0 ° (angle) and 0 g / l (concentration). Measurements were carried out at concentrations of 2.5 g / l, 5 g / l and 7.5 g / l and in the angular range 15-145 °. The sample was dissolved at 90 ° C and diluted at room temperature to the appropriate concentration. Subsequently, the individual concentrations were filtered through 0.45 μm filter and measured immediately. The resulting molecular weight for a H1 micelle was 59,000 Da.

Using molecular modeling, with an average molecular weight of 59,000 Da (as determined by SLS) for an H1 micelle and n = 6, the micelle contains about 18 H1 molecules and the average molecular weight is 3300 g / mol is.

7. Effectiveness of the compounds of the invention

7.a. Stabilizing effect in LDPE

A mixture of LDPE (Lupolen 1840 D from Lyondellbasell, Netherlands) and 0.2% by weight HAS compounds was homogenized in a Berstorff twin-screw extruder (melt temperature: 180 ° C.) and then granulated. The granules thus obtained were then extruded in a blown film to 100 micron thick films. The films were then artificially weathered according to the standard DIN EN ISO 4892-2, wherein the elongation at break was determined as a measure of the mechanical stability of the films was measured. Table 3 summarizes the measurement results:

Table 3:

^* The concentration of active groups in the polymer. The active part of the molecule is the tetramethylpiperidine moiety.

In the stabilizer, the concentration is:

H1: 1, 93 mmol / g,

VH2: 3.34 mmol / g,

VH7: 3.53 mmol / g

The example shows that, when the concentration of the active moiety in the plastic is significantly lower, the compound H1 used according to the invention provides a better stabilizing effect in comparison with the comparative compounds VH2 or VH3.

7.b. Influence on the heat-adhesive properties:

40 m LDPE / EVA films containing 0.1, 0.2 or 0.5% HAS compound were heat-sealed and measured after 45 days of storage at room temperature, the tensile strength according to DIN in N / mm ² . The results are given in Table 4:

Table 4:

nb not determined

The results in Table 4 show that in H1 compared to the comparative compound VH2 has virtually no negative impact on the tensile strength. Ie influence on water carry-over and production speed in film production:

Plastic compounds containing the HAS compound (0.4% strength) indicated in Table 5 with LLDPE were melted in a single-screw extruder and extruded through a slot die. The hot polymer melt was cooled by passing it through a water bath, whereby the withdrawal speed could be adjusted by a roller after the water bath. The take-off speed was adjusted so that no more water was torn out of the bath, and the maximum achievable production rates are shown in Table 5:

Table 5:

7.d. Influence on base-sensitive pigments:

A mixture of 67 parts LLDPE, 5 parts Luwax A powder, 8 parts Paliotol Yellow K 1841 and 20 parts of the respective HAS were processed in a twin-screw extruder to a masterbatch. To examine the purtone, the master batches were mixed with HDPE in a concentration of 25% and processed into 2 mm thick injection-molded parts in an injection molding machine. The plastic temperature was kept at 260 ^° C. for 5 minutes prior to spraying in order to simulate a thermal load. For lightening, 12.5% of the batches were mixed with 1% titanium dioxide and HDPE and treated as well.

The color deviation after 5 minutes of temperature treatment at 260 ⁰ C was determined as ΔE. The results are shown in Table 6.

Table 6:

As can be seen from Table 6, the influence of H1 on the color stability of the base-sensitive pigment is significantly lower than that of the comparative compounds VH1 and VH2.

7.e Improved solubility in non-polar media

The solubility in non-polar solvents was determined in g / 100g solvent at 20 ⁰ C. The results are shown in Table 7.

Table 7:

7.f Influence on sulphurous soot

3 g of carbon black with a sulfur content of 0.69% (Elftex 415, Cabot Corporation) were weighed together with 3 g of the respective HAS into a headspace GC vial and thoroughly mixed by shaking. Through the septum a cannula with 0.45μm syringe filter and Dräger tube (range 0.2 to 5 ppm) was introduced. The samples were annealed for 20 minutes in an oil bath at 220 ⁰ C.

Only soot:

There was no discoloration of the Dräger pad found.

Carbon black with VH2:

After 10 minutes, the tube begins to stain beige from the bottom up, indicating the formation of H2S. After 18 minutes, the tube is colored through (> 5 ppm). It was not flushed with air, but only measured by self-pressure gas.

Carbon black with H1:

After 20 minutes, only one staining was observed up to the 0.2 ppm level.

Claims

 claims:

Polymer composition containing

(i) at least one polyolefin as or in the continuous phase; and (ii) at least one amphiphilic additive present in the continuous phase at least partially in the form of spherical self-organics and wherein the self-organizates have an average diameter of less than 200 nm.

The polymer composition of claim 1, wherein the amphiphilic additive is a sunscreen or a mixture of sunscreens.

A polymer composition according to claim 1 or 2, wherein the light stabilizer is a copolymer containing polymerized repeating units of an α-olefin and an α, β-ethylenically unsaturated compound having a hindered amine group.

A polymer composition according to claim 3, wherein the copolymer is an oligomeric compound containing repeating units of the formula (I)

wherein

R ^{1 is} hydrogen;

R ^{2 is} hydrogen or C ₁ -C ₃ 2-alkyl;

R ^{3 is} hydrogen or C ₁ -C ₃ 2-alkyl;

R ⁴ is Ci6-C _{3 is} 2-alkyl;

R ⁵ for a tetramethylpiperidinyl radical of the formula (II)

stands; in which R ^{6 is} hydrogen, d-Ce-alkyl or an O-radical (-O ^» ), wherein at most 60 mol% of the radicals R ⁶ may be an O-radical; and

is -C (= O) O-, -OC (= O) -, -O- or -C (= O) N (R ⁷ ) -, wherein

R ^{7 is} hydrogen or C ₁ -C ₆ -alkyl,

or

R ¹ together with UR ⁵ for a radical of the formula

stands, where

# indicates the linkage to the copolymer backbone; and

R ^{5 * has} the meaning given for R ⁵ .

5. Polymer composition according to claim 4, wherein the copolymer is an oligomeric compound of formula (1.1),

)

wherein n is an integer of 5 to 15; R ⁴ is Ci6-C _{3 is} 2-alkyl;

R ^{6 is} hydrogen, a C 1 -C ⁶ -alkyl group or an O-radical (-O), where not more than 60% by mol of the radicals R ⁶ may be an O-radical.

6. A polymer composition according to claim 5, wherein R ⁴ in formula (1.1) is C 16 -C 22 alkyl.

7. A polymer composition according to claim 5 or 6, wherein R ⁶ in formula (1.1) is hydrogen or C 1 -C ₄ -alkyl.

8. The polymer composition according to any one of claims 1 or 2, wherein the light stabilizer is a monomeric compound of formula (XII),

wherein

R ^{5 is} a tetramethylpiperidinyl radical of formula II;

wherein R ^{6 is} hydrogen, C ₁ -C ₆ -alkyl or an O-radical (-O *), wherein at most 60 mol% of the radicals R ⁶ may be an O-radical; R ^{10 is} hydrogen; R ¹¹ -C ₃ 2-alkyl, hydrogen or C _6; R ^{12 is} hydrogen or C ₆ -C ₃₂ alkyl;

R ¹³ -C ₃ 2-alkyl, hydrogen or C _6; R ¹⁴ is Ci6-C ₃₂ alkyl or C ₆ -C ₃₂ - alkyl-C (= O); and X is O or NH;

or

R ¹⁰ together with XR ^{5 represents} a radical of the formula (XIII)

where # denotes the linkage with the carbon atom which carries the radicals R ¹¹ and R ¹² , ^* denotes the linkage to the carbonyl carbon atom and R ^{5 * has} the meaning given for R ⁵ .

A polymer composition according to claim 8, wherein the monomeric light stabilizer of formula (XII) is a compound of formula (XII.1),

)

wherein

R ¹¹ -C ₃ 2-alkyl, hydrogen or C _6;

R ¹² -C ₃ 2-alkyl, hydrogen or C _6;

R ¹³ -C ₃ 2-alkyl, hydrogen or C _6;

R ^{14 is} C 16 -C ₃₂ alkyl; R ^{6 is} hydrogen, a Ci-C6-alkyl group or an O-radical (-O), wherein at most 60 mol% of the radicals R ⁶ may be an O-radical.

10. A polymer composition according to claim 8, wherein the monomeric light stabilizer is a compound of formula (XII.2),

wherein

X is O or NH; R ^{10 is} hydrogen; R ^{11 is} hydrogen or C 16 -C ₃₂ -alkyl; R ¹² -C ₃ 2-alkyl, hydrogen or C _6;

R ¹³ -C ₃ 2-alkyl, hydrogen or C _6;

R ¹⁴ is Ci6-C ₃₂ alkyl or C ₆ -C ₃₂ - alkyl-C (= O);

R ^{6 is} hydrogen, a Ci-C6-alkyl group or an O-radical (-O), wherein at most 60 mol% of the radicals R ⁶ may be an O-radical.

1 1. A polymer composition according to any one of the preceding claims, wherein the spherical self-organysates have hydrophilic groups inside and hydrophobic groups outside.

12. A polymer composition according to any one of the preceding claims, wherein the spherical self-organizates have an average diameter of less than 50 nm

13. Polymer composition according to one of the preceding claims, wherein the average distance between the spherical self-organizates in a range of 40 to 200 nm, preferably 50 to 100 nm.

14. A polymer composition according to any one of the preceding claims wherein the average total molecular weight of the spherical self-assembly is 15,000 to 100,000

Dalton is.

15. A polymer composition according to any one of the preceding claims, wherein the polyolefin is selected from homo- and copolymers of ethylene and homo- and copolymers of propylene.

16. Polymer composition according to one of the preceding claims, additionally comprising at least one metal salt of a C7-C _o-3 carboxylic acid, preferably a metal salt of stearic acid or behenic acid, in particular calcium stearate, calcium behenate, zinc behenate containing or zinc stearate.

17. Polymer composition according to one of the preceding claims, containing at least one of the amphiphilic additive ii) different additive.

18. The polymer composition according to claim 17, wherein the additive other than the amphiphilic additive ii) is selected from colorants, lubricants, antioxidants, light stabilizers, antistatics, flame retardants, nucleating agents, pigment dispersants, biocides and fillers and reinforcing agents.

A polymer composition according to claim 18, wherein the light stabilizer other than the amphiphilic additive ii) is selected from compounds containing recurring units of the formula (XIV)

wherein n is an integer of 1 to 100; and

Compounds of the formula (XV)

wherein

X is O or NH;

R ^{15 is} C 16- C ₃ 2-alkyl; and

R ^{16 is} hydrogen, a d-Cβ-alkyl group or an O-radical (-O), wherein less than 30 mol% of the radicals R ¹⁶ may be an O-radical.

20. A process for the preparation of a polymer composition as defined in any one of claims 1 to 19, wherein the polyolefin plasticized and in the plasticized state with the amphiphilic additive (ii) brings into intimate contact and at the same time or subsequently admits the optionally present additives.

21. The method according to claim 20, wherein the plasticizing takes place in an extruder.

22. Use of a polymer composition as defined in any one of claims 1 to 19, for the production of moldings, films and fibers, in particular for the production of agricultural films.

23. agricultural film containing or consisting of a polymer composition according to any one of claims 1 to 19.

24. Method of plant culture, wherein one (i) a crop at least partially with an agricultural sheet according to claim

23 surrounds; and (ii) once the crop plant or treated repeatedly with an agricultural chemical, wherein the agricultural chemical or the microbial metabolite has a pK _s value of less than 15.74 at 25 ⁰ C.

25. Use of an agricultural film according to claim 23 in a plant culture which comes into contact with acidic compounds.