RU2800783C1 - Light stabilizer mixture for polyolefin film, tape or monothread - Google Patents

Abstract

FIELD: chemical industry.

SUBSTANCE: invention is aimed at reducing the water carryover of a light-stabilized polyolefin film, tape or fibre that contains component (A) as a light stabilizer and which passes through a water bath during production, while the polyolefin film, tape or monofilament additionally contains component (B) as a light stabilizer, an example of component (A) is

,

where E₁ represents ,

E₂ is and a₃ is a number from 2 to 10, and an example of component (B) is

.

EFFECT: reducing the water carryover.

3 cl, 4 tbl, 4 ex

Description

The present invention relates to a method for reducing water carryover of a light stabilized polyolefin film, tape or monofilament which passes through a water bath during production, to a polyolefin film, tape or monofilament obtained according to said method, and to the use of specific light stabilizers to reduce water carryover of a light stabilized polyolefin film, ribbons or monofilament.

A common method for producing polyolefin films, tapes or monofilaments is to extrude the polymer melt through a suitable device, in the form of a film, tape or monofilament, into a water bath where the film, tape or monofilament is cooled and solidified. Then the film, tape or monofilament, in turn, can be removed from the water bath and subjected to further processing steps. When leaving the water bath, the film, tape or monofilament can trap water, which interferes with subsequent processing steps. This effect, water bath entrainment, is often referred to as "water entrainment" in the technical literature, and the abbreviation WCO can be used for this.

Stretching the film at the appropriate temperature leads to orientation and further crystallization of the polymer, resulting in specific properties. This second processing step may take place directly on the film, but the primary film is often stripped into strips prior to the stretching process. Since the required properties are obtained during the stretching process, it is important that all process parameters are followed exactly. Even traces of moisture on the film or on the tapes before the stretching process change the subsequent stretching and orientation, creating very serious changes in the quality of the resulting product. The consequences of this are not limited to the corresponding significant changes in the quality of the end product obtained. Even in the course of receiving or processing, poor quality can cause the tapes to break, for example, and thus stop production. A source of water that can lead to these problems is the cooling bath into which the primary film is extruded. Although most plastics, in particular polyolefins such as polyethylene (PE) or polypropylene (PP), are very hydrophobic and therefore have little tendency to absorb water, it is often found that at relatively high production rates, water droplets or a thin film of water adhere to the film, when it is stretched over a water bath. In addition, various additives, such as light stabilizers, must be added to the polymer to ensure that the final product has good functionality. Some of these additives contribute to an increased carryover of water from the water bath. Additives, as well as maximum processing speed, are essential if suitable products are to be produced at a low cost. Reducing the processing speed leads to non-economic production. In addition, it is not possible to avoid adding the necessary additives, some of which lead to a deterioration in WCO (i.e. higher WCO and therefore a poorer product), because otherwise the properties of the product caused by the additives cannot be achieved.

At present, the reduction of WCO is carried out through the simplest design measures in the course of machine production. For example, pulling a film out of a water bath is generally done vertically upwards, so that only gravity maximizes the amount of water falling down. In addition, pinch rollers and/or air knives are often used to remove as much water from the film as possible. There are other technical methods depending on the specific configuration of the machine.

There is still a need for a WCO improvement process in the production of polyolefin films, tapes and monofilaments. Ideally, no unwanted side effects should occur, and the method should also be capable of using existing drugs without problems.

Surprisingly, it has been found that the addition of a certain second hindered amine light stabilizer to a light stabilized polyolefin film, tape, or monofilament that already contains a hindered amine light stabilizer can markedly reduce WCO during production. This is unexpected, especially since the two hindered amines belong to the same class of compounds. It was completely unexpected and by no means predictable that specific combinations of two hindered amine light stabilizers show a synergistic improvement in WCO properties.

Thus, the present invention provides a method for reducing water carryover of a light stabilized polyolefin film (preferably a monolayer), tape (preferably a monolayer) or monofilament, which contains component (A) as a light stabilizer and which passes through a water bath during production, characterized in that the polyolefin the film, tape or monofilament additionally contains component (B) as a light stabilizer,

component (A) is at least one compound selected from the group consisting of compounds of formula (A-I), compounds of formula (A-II) and compounds of formula (A-III),

where A ₁ represents hydrogen or C ₁ -C ₄ alkyl,

A ₂ is a direct bond or C ₁ -C ₁₀ alkylene, and

a ₁ is a number from 2 to 20;

where A ₃ , A ₄ and A ₅ independently of each other are C ₂ -C ₁₈ alkylene,

A ₆ , A ₇ , A ₈ , A ₉ and A ₁₀ independently of each other represent hydrogen, C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl or a group of formula (a-1),

radicals A ₁₁ independently of each other represent hydrogen, C ₁ -C ₁₂ alkyl or C ₅ -C ₁₂ cycloalkyl, and

and ₂ is a number from 1 to 20;

where A ₁₂ represents C ₂ -C ₁₈ alkylene, C ₅ -C ₇ cycloalkylene or C ₁ -C ₄ alkylenedi(C ₅ -C ₇ cycloalkylene),

A ₁₃ and A ₁₄ independently of each other represent hydrogen, C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl or a group of formula (a-2),

or radicals A ₁₃ and A ₁₄ , together with the nitrogen atom to which they are bonded, form a 5-10-membered heterocyclic ring,

radicals A ₁₅ are independently hydrogen, C ₁ -C ₁₂ alkyl or C ₅ -C ₁₂ cycloalkyl, and

and ₃ is a number from 2 to 20;

component (B) is at least one compound selected from the group consisting of compounds of formula (B-I), compounds of formula (B-II), compounds of formula (V-III) and compounds of formula (B-IV),

where R ₁ is C ₁ -C ₁₈ alkyl, C ₁ -C ₁₈ hydroxyalkyl, cyclohexyl or hydroxycyclohexyl, or R ₁ is -C(C ₆ H ₅ )(H)CH ₂ -OH and R ₂ is C ₁ -C ₂₅ alkyl or a group of formula (b-1);

where x is an integer from 2 to 8 and y is zero or 1;

where R ₃ represents C ₂ -C ₁₈ alkylene, C ₅ -C ₇ cycloalkylene or C ₁ -C ₄ alkylenedi(C ₅ -C ₇ cycloalkylene),

radicals R ₄ independently of each other represent C ₁ -C ₁₂ alkyl or C ₅ -C ₁₂ cycloalkyl,

R ₅ and R ₆ independently of each other represent hydrogen, C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl or a group of formula (b-2),

or the radicals R ₅ and R ₆ , together with the nitrogen atom to which they are attached, form a 5-10 membered heterocyclic ring and

b ₁ is a number from 1 to 20;

where the radicals R ₈ , R ₉ and R ₁₀ independently of each other represent C ₂ -C ₁₈ alkylene, and the radicals R ₇ independently of each other represent a group of formula (b-3)

where R ₁₁ and R ₁₂ independently of each other represent hydrogen, C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl or a group of formula (b-4)

and the radicals R ₁₃ are independently C ₁ -C ₁₂ alkyl or C ₅ -C ₁₂ cycloalkyl;

Where

R ₅ is C ₁ -C ₂₅ alkyl,

n is a number from 1 to 10, and

W is a wax residue containing from 50 to 1000 carbon atoms, preferably a polyethylene or polypropylene wax residue.

Components (A) and (B) are preferably in the same layer if the film is a multilayer film.

The compounds of components (A) and (B) are known and widely commercially available and can be prepared according to known methods.

Compounds of component (A) can be prepared analogously to the methods described in US-A-4,233,412, US-A-4,477,615 (CAS 136,504-96-6) and US-A-4,108,829, US-A-4,086,204, US-A-4,331,586 , US-A-6,046,304 and US-A-6,297,299.

Component (B) compounds can be prepared analogously to the methods described in US-A-6,388,072, US-A-6,117,995, US-A-6,420,462 and US-A-6,677,451, and US-A-5,844,026.

Preferred compounds of component (A) are the commercial products ^Tinuvin® 622, ^Sabostab® UV 119, ^Uvasorb® HA88, ^Uvasorb® HA10, ^Chimassorb® 944, ^Chimassorb® 2020, ^Cyasorb® UV 3346, ^Cyasorb® UV 3529 and ^Dastib® 1082.

Preferred compounds of component (B) are the commercial products ^Tinuvin® NOR 371, ^Tinuvin® 123, ADK ^STAB® LA81 or Flamestab® ^NOR 116.

The polyolefin is preferably polyethylene or polypropylene and contains, for example, from 0.01 to 10%, in particular from 0.1 to 1%, based on the weight of the polyolefin, of the sum of components (A) and (B).

The weight ratio of component (A) to component (B) is, for example, 1:20 to 20:1, preferably 1:15 to 15:1.

The values of the end groups that saturate the free valencies in compounds (A-I), (A-II), (A-III) and (B-II) depend on the processes used to obtain them. The end group can also be changed after the compounds have been prepared.

When compounds of formula (A-I) are obtained, for example, by reacting a compound of formula

in which A ₁ is hydrogen or methyl, with a dicarboxylic acid diester of the formula Y ₀ -OOC-A ₂ -COO-Y ₀ , in which Y ₀ is, for example, methyl, ethyl or propyl, and A ₂ has values as defined above, the end group associated with the 2,2,6,6-tetramethyl-4-oxypiperidin-1-yl radical is hydrogen or -CO-A ₂ -COO-Y ₀ , and the end group associated with a diacyl radical, is -OY ₀ or

In compounds of formula (A-II), the end groups attached to the triazine radical are, for example, Cl or the group

and the end group associated with the amino radical is, for example, hydrogen or a group

When compounds of formula (A-III) are obtained by reacting compounds of formula

in which X ₀ represents, for example, halogen, in particular chlorine, and A ₁₃ and A ₁₄ have the meanings as defined above, with a compound of the formula

in which A ₁₂ and A ₁₅ have the meanings as defined above, the end group associated with the diamino radical is, for example, hydrogen or

and the end group associated with the triazine radical is, for example, X ₀ or

If X ₀ is halogen, it is preferred to replace it with, for example, -OH or an amino group when the reaction is complete. Examples of amino groups which may be mentioned are pyrrolidin-1-yl, morpholino, -NH ₂ , -N(C ₁ -C ₈ )alkyl) ₂ and -NR ₀ (C ₁ -C ₈ alkyl) in which R ₀ represents hydrogen or a group of formula (a-2).

One particularly preferred compound of formula (A-III) is

where E ₁ represents , E ₂ is and a ₃ is a number from 2 to 10.

The preparation of this compound is described in Example 10 in US-A-6,046,304.

In compounds of formula (B-II), the end group associated with the diamino radical is, for example, hydrogen or

and the end group associated with the triazine radical is, for example,

Examples of alkyls having up to 25 carbon atoms are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3- dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethyl- hexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.

Examples of C ₃ -C ₁₂ cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl. Cyclohexyl is preferred.

Examples of alkylene having up to 18 carbon atoms are methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, decamethylene and octadecamethylene.

A preferred example of C ₅ -C ₇ cycloalkylene is cyclohexylene.

A preferred example of C ₁ -C ₄ alkylenedi(C ₅ -C ₇ cycloalkylene) is cyclohexylene-methylene-cyclohexylene.

A preferred example of a 5-7 membered heterocyclyl ring is a morpholine group.

In the preferred method, A ₁ is hydrogen,

A ₂ is C ₂ -C ₆ alkylene, and

a ₁ is a number from 2 to 10;

A ₃ , A ₄ and A ₅ independently of each other are C ₂ -C ₆ alkylene,

A ₆ , A ₇ , A ₈ , A ₉ and A ₁₀ independently of each other are C ₁ -C ₄ alkyl,

radicals A ₁₁ are independently hydrogen or C ₁ -C ₄ alkyl, and

and ₂ is a number from 1 to 10;

A ₁₂ is a C ₂ -C ₆ alkylene,

A ₁₃ and A ₁₄ independently of each other represent hydrogen, C ₁ -C ₄ alkyl, cyclohexyl or a group of formula (a-2),

or radicals A ₁₃ and A ₁₄ , together with the nitrogen atom to which they are bonded, form a morpholino group,

radicals A ₁₅ are independently hydrogen or C ₁ -C ₄ alkyl, and

and ₃ is a number from 2 to 10,

R ₁ is C ₁ -C ₁₁ alkyl or C ₂ -C ₆ hydroxyalkyl, R ₂ is C ₁₀ -C ₂₀ alkyl or a group of formula (b-1);

R ₃ is C ₂ -C ₆ alkylene,

radicals R ₄ independently of one another represent C ₁ -C ₄ alkyl or cyclohexyl;

R ₅ and R ₆ independently of each other represent hydrogen, C ₁ -C ₄ alkyl, cyclohexyl or a group of formula (b-2),

or the radicals R ₅ and R ₆ , together with the nitrogen atom to which they are attached, form a morpholino group and

b ₁ is a number from 1 to 10;

R ₈ , R ₉ and R ₁₀ independently of each other represent C ₂ -C ₆ alkylene and the radicals R ₇ independently of each other represent a group of formula (b-3),

R ₁₁ and R ₁₂ are independently C ₁ -C ₄ alkyl, and R ₁₃ are independently C ₁ -C ₄ alkyl or cyclohexyl.

According to a preferred embodiment of the present invention, the compound of formula (A-I) corresponds to the formula (A-I-1)

where a ₁ is a number from 2 to 10,

a compound of formula (A-II) corresponds to formula (A-II-1) or (A-II-2),

where a ₂ is a number from 1 to 10,

where a ₂ is a number from 1 to 10,

the compound of formula (A-III) corresponds to the formula (A-III-1), (A-III-2), (A-III-3) or (A-III-4),

where a ₃ is a number from 2 to 10,

where a ₃ is a number from 2 to 10,

where A ₁₅ is hydrogen or methyl and a ₃ is a number from 2 to 10,

where a ₃ is a number from 2 to 10.

the compound of formula (B-I) corresponds to the formula (B-I-1), (B-I-2) or (B-I-3),

the compound of formula (B-II) corresponds to the formula (B-II-1),

where b ₁ is a number from 1 to 10,

a compound of formula (B-III) corresponds to formula (B-III-1),

where R ₇ represents a group of formula (b-3-1).

According to a particularly preferred embodiment of the present invention, component (A) is a compound of formula (A-I-1) and component (B) is a compound of formula (B-II-1), or

component (A) is a compound of formula (A-II-1-a) and component (B) is a compound of formula (B-III-1), or

component (A) is a compound of formula (A-III-2) and component (B) is a compound of formula (B-I-1),

where a ₁ is a number from 2 to 10,

where X is a group And

Y is a group

where a ₃ is a number from 2 to 10,

where b ₁ is a number from 1 to 10,

where R ₇ represents a group of formula (b-3-1).

The polyolefin may further comprise one or more conventional additives. Suitable examples are listed below.

1. Antioxidants

1.1. Alkylated monophenols, e.g. 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, -tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethylphenol, 2 ,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in side chains, e.g., 2,6-di -nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2 ,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, e.g.

1.3. Hydroquinones and alkylated hydroquinones, e.g. , 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.

1.4. Tocopherols, eg α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

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

1.6. Alkylidenebisphenols, e.g. 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), -6-(α-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis( 4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenbis(6-tert-butyl-4-isobutylphenol), 2,2 '-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6- di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2.6 -bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1- bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis (3-tert-butyl-4-hydroxy-5-methyl-phenyl)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-hydroxy2-methylphenyl)-4-t-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. O-, N- and S-benzyl compounds, e.g. tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6- dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

1.8. Hydroxybenzylated malonates e.g. 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.

1.9. Aromatic hydroxybenzyl compounds, e.g. 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, -butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine compounds such as 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1, 3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di -tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di -tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine , 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

1.11. Benzylphosphonates e.g. dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.

1.12._Acylaminophenols, e.g. 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. methanol, ethanol, n-octanol, iso-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-thioundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of 3-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. methanol, ethanol, n-octanol, iso-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-thioundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

1.15. Esters of β-3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thioundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha -2,6,7-trioxabicyclo[2.2.2]octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydric alcohols, e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexane iol, 1,9-nonand iol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thioundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, e.g. N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N' -bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide, N,N-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N'-bis[2- (3-[3,5-di-t-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide ( ^Naugard® XL-1, supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

1.19. Amine antioxidants, e.g. N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine , N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, 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, e.g. 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(phenyl-amino)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-octyldiphenylamines, mixture of mono- and dialkylated nonyldiphenylamines, mixture of mono- and dialkylated dodecyldiphenylamines, mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, mixture mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl / tert-octylphenothiazines, a mixture of mono- and dialkylated tert- octylphenothiazines, N-allylphenothiazine, N,N,N,N'-tetraphenyl-1,4-diaminobut-2-ene.

2. UV absorbers and light stabilizers

2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, e.g. 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3',5'-di-t-butyl-2'-hydroxyphenyl)benzotriazole 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5 '-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole, 2-( 3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl -2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro -benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy- 5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5 '-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxy-phenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert- butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; transesterification product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO-CH2CH2-]2-, where R is 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-hydroxy-3'- (α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole; 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)phenyl]benzotriazole.

2.2. 2-Hydroxybenzophenones, e.g. dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, e.g. -butyl-4-hydroxybenzoate, hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate, octadecyl-3,5-ditert-butyl-4-hydroxybenzoate, 2-methyl-4,6-ditert-butylphenyl-3,5 -ditert-butyl-4-hydroxybenzoate.

2.4. Acrylates e.g. -methyl-p-methoxy-cinnamate, methyl α-carbomethoxy-p-methoxycinnamate, N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline, neopentyl tetra(α-cyano-β,β-diphenyl acrylate.

2.5. Nickel compounds, e.g. 2,2'-thiobis-[4-(1,1,3,3-tetramethylbutyl)phenol] nickel complexes such as a 1:1 or 1:2 complex with or without additional ligands such as as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, e.g. hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole with or without additional ligands.

2.6. Hindered amines, e.g. (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, condensate 1-(2 -hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates 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-tetra-methyl- 4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1,11,2-ethandiyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine , 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert -butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione, bis(1-octyloxy-2,2,6 ,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or cyclic N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl) condensates hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1 condensate, 3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1 condensate ,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]decan-2 ,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6 -pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N,N'-bis(2,2,6,6 -tetramethyl-4-piperidyl)hexamethylene diamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensate of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1 ,3,5-triazine, as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. no. [136504-96-6]); condensate of 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine, N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268 -64-7]); 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-oxo-spiro[4,5]decane, reaction product 7,7,9,9-tetramethyl-2-cycloundecyl-1- oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl )ethene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, diester of 4-methoxymethylenemalonic acid and 1,2,2,6, 6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-hydroxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]sloxane, reaction product of a copolymer of maleic anhydride and α-olefin with 2,2, 6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine, 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4 -yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1,3,5-triazine, 1-(2-hydroxy-2-methylrhoroxy)-4-octadecanoyloxy-2,2,6,6- tetramethylpiperidine 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvor (Clariant; CAS Reg. no. 106917-31-1], 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, reaction product of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidine -4-yl)butylamino]-6-chloro-s-triazine with N,N'-bis(3-aminopropyl)ethylenediamine), 1,3,5-tris(N-cyclohexyl-N-(2,2,6 ,6-tetramethylpiperazin-3-on-4-yl)amino)-s-triazine, 1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperazin-3-one -4-yl)amino)-s-triazine.

2.7. Oxamides, e.g. 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and mixtures thereof with 2-ethoxy-2' -ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.

2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy- 4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 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-butyloxyrhoroxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]- 4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxyrhoroxy)-2-hydroxyphenyl]-4,6-bis(2,4 -dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxyrhoroxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3, 5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1 ,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-horoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4 -(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4, 6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4-methoxyphenyl)-1,3, 5-triazine, 2-(4,6-bis-biphenyl-4-yl-1,3,5-triazin-2-yl)-5-(2-ethyl-(n)-hexyloxy)phenol.

3. Metal deactivators, e.g. N,N'-diphenyloxamide, N-salicilal-N'-salicyloylhydrazine, N,N'-bis-(salicyloyl)hydrazine, N,N'-bis-(3,5-ditert-butyl) -4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis-(benzylidene)oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, seba-cylbisphenylhydrazide, N,N'-diacetylamino-1,2,4-dihydrazide, N,N'-bis-(salicyloyl )oxalyldihydrazide, N,N'-bis-(salicyloyl)thiopropionyldihydrazide.

4. Phosphites and phosphonites e.g. , bis (2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diiso-decyloxypentaerythritol diphosphite , bis(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearylsorbitol triphosphite, tetrakis(2,4-di-tert -butylphenyl) 4,4'-biphenylene diphosphite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin, bis(2, 4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert- butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocin, 2,2',2"-nitrilo[triethyltris(3,3',5,5'-tetra-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, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.

Particular preference is given to the use of the following phosphites:

Tris(2,4-di-tert-butylphenyl)phosphite ( ^Irgafos® 168, Ciba Specialty Chemicals Inc.), tris(nonylphenyl)phosphite,

5. Hydroxylamines, e.g. N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N- hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tall oil amines.

6. Nitrones, for example, N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl- alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrones derived from N, N-dialkylhydroxylamines derived from hydrogenated tall oil amines.

7. Thiosynergists, eg dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis[3-(dodecylthio)propionate] or distearyl disulfide.

8. Peroxide scavengers, e.g. itrite.

9. Polyamide stabilizers, for example, copper salts in combination with iodides and/or phosphorus compounds and divalent manganese salts.

10. Principal common stabilizers, e.g. melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and salts of alkaline earth metals and higher fatty acids, in particular calcium stearate, zinc stearate, behenate magnesium, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony antimony pyrocatecholate or zinc pyrocatecholate.

11. Nucleating agents, for example inorganic compounds such as talc, metal oxides such as titanium dioxide and magnesium oxide, phosphates, carbonates and sulfates, preferably alkaline earth metals; organic compounds such as mono- and polycarboxylic acids and their salts such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate and sodium benzoate; polymeric compounds, in particular ionic copolymers ("ionomers"). Especially preferred are 1,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1,3:2,4-di(p-methyldibenzylidene)sorbitol, and 1,3:2,4-di(benzylidene) sorbitol.

12. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibers, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers

13. Other additives such as plasticizers, lubricants, emulsifiers, pigments, rheology modifiers, catalysts, leveling aids, optical brighteners, flame retardants, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, such as those described in U.S. 4,325,863; U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A-4316611;

DE-A-4316622; DE-A-4316876; EP-A-0589839, EP-A-0591102; EP-A-1291384 or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2 -stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5.7 -di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2-acetyl-5-isooctylphenyl)-5-isooctylbenzofuran-2-one.

The weight ratio of component (A) to standard additive is, for example, 1:100 to 100:1, preferably 1:100 to 10:1, in particular 1:10 to 10:1.

According to a preferred embodiment of the present invention, the polyolefin further comprises, as component (C), a phenolic antioxidant, preferably octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

Component (C) may be present in a concentration of, for example, 0.01 to 10%, based on the weight of the polyolefin.

According to another preferred embodiment of the present invention, component (A) is a compound of formula (A-I-1) and a compound of formula (A-III-2), and component (B) is a compound of formula (B-I-1) or (B-II -1), and the polyolefin optionally contains octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.

Another object of the present invention is a polyolefin film, tape or monofilament obtained according to the method described above.

Another object of the present invention is the use of component (B) as a light stabilizer for reducing water carryover of a light stabilized polyolefin film, tape or monofilament which contains component (A) as a light stabilizer and which passes through a water bath during production.

Another object of the present invention is a method for producing a light-stabilized polyolefin film, tape or monofilament, comprising the step of passing said light-stabilized polyolefin film, tape or monofilament through a water bath at a withdrawal speed from the extruder from 5 to 100 m/min, preferably from 4 to 80 m/min. min or from 10 to 50 m/min, in particular from 20 to 40 m/min, characterized in that said polyolefin film, tape or monofilament contains components (A) and (B) as defined above. All of the above preferences also apply to this method, which is useful for reducing water bath carryover.

The examples below illustrate the invention in more detail. All percentages and parts are by weight unless otherwise noted.

Light stabilizers used in the following examples:

Connection (A-I-1):

( ^Tinuvin® 622)

where a ₁ is a number from 2 to 10.

Compound (A-II-1-a):

( ^Sabostab® UV119)

where X is a group And

Y is a group

Compound (A-III-2):

( ^Chimasorb® 2020)

where E ₁ represents , E ₂ is and a ₃ is a number from 2 to 10.

Connection (B-I-1):

Compound (B-II-1):

where E ₃ represents , E ₄ is and where b ₁ is a number from 2 to 10.

Compound (B-III-1):

(Flamestab ^® NOR 116)

where R ⁷ is a group of formula

Definition of synergy for the experiments below:

The synergistic effect of the WCO (water carryover) of the two light stabilizers (α) and (β) is determined by comparing the expected WCO values with the actually measured WCO activity values. Expected values are calculated based on the law of additivity (B. Ranby and J.F. Rabek; Photodegradation, Photo-oxidation and Photostabilization of Polymers, Principles and Applications, John Wiley & Sons, London, New York, Sydney, Toronto, 1975, pages 418 and 419) according to the following equation for a 1:1 ratio of two light stabilizers:

There is a synergistic WCO effect of the two light stabilizers in the samples below when "measured WCO" < "calculated WCO" (low WCO values are desirable).

The above equation is adapted appropriately when the ratio of the two light stabilizers is other than 1:1, for example, if the ratio is 2:1, the expected WCO effect can be calculated according to the following equation:

Example 1:

The light stabilizers indicated in tables 1a and 1b are mixed in a high speed mixer (MTI, Mischtechnik International, Germany) with polyethylene (Dowlex®SC 2108). The mixture is extruded at 200° C. in a twin screw extruder (Krauss Maffei Berstorff, Germany) to obtain granules, which are then converted in a pilot extruder (Leonard, Italy) into ribbons at 220° C. Water entrainment is expressed in terms of the length (mm) that the water from the water cooling bath is carried along with the extrudate (200 microns) before entering the draw section. The lower the water carryover, the faster and more economically the film, stretched tape or monofilament is processed. The results are shown in tables 1a and 1b.

Example 2:

The light stabilizers indicated in tables 2a and 2b are mixed in a high-speed mixer (MTI, Mischtechnik International, Germany) with polyethylene (Dowlex®SC 2108), which contains 0.5 wt. % relative to the mass of polyethylene, compounds (A-I-1). The mixture is extruded at 200° C. in a twin screw extruder (Krauss Maffei Berstorff, Germany) to obtain granules, which are then converted in a pilot extruder (Leonard, Italy) into ribbons at 220° C. Water entrainment is expressed in terms of the length (mm) that the water from the water cooling bath is carried along with the extrudate (200 microns) before entering the draw section. The lower the water carryover, the faster and more economically the film, stretched tape or monofilament is processed. The results are shown in tables 2a and 2b.

Example 3:

The light stabilizers indicated in tables 3a and 3b are mixed in a high speed mixer (MTI, Mischtechnik International, Germany) with polypropylene ( ^Polychim® A 10 TB). The mixture is extruded at 230° C. in a twin screw extruder (Krauss Maffei Berstorff, Germany) to obtain granules, which are then converted in a pilot extruder (Leonard, Italy) into ribbons at 240° C. Water entrainment is expressed in terms of the length (mm) that the water from the water cooling bath is carried along with the extrudate (240 microns) before entering the draw section. The lower the water carryover, the faster and more economically the film, stretched tape or monofilament is processed. The results are shown in tables 3a and 3b.

Example 4:

The light stabilizers indicated in table 4 are mixed in a high-speed mixer (MTI, Mischtechnik International, Germany) with polyethylene (Dowlex ^® SC 2108), which contains 0.5 wt. %, relative to the mass of polyethylene, compounds (AI-1). The mixture is extruded at 200° C. in a twin screw extruder (Krauss Maffei Berstorff, Germany) to obtain granules, which are then converted in a pilot extruder (Leonard, Italy) into ribbons at 220° C. Water entrainment is expressed in terms of the length (mm) that water from the water cooling bath is carried along with the extrudate (100 microns) before entering the draw section. The lower the water carryover, the faster and more economically the film, stretched tape or monofilament is processed. The results are shown in Table 4.

In the above examples, "%" means "wt.% relative to the weight of the polyolefin".

Claims (10)

1. Mixture of light stabilizers for polyolefin film, tape or monofilament, including compounds of formula (A-I-1) and formula (A-III-2), in combination with a compound of formula (B-I-1) or a compound of formula (B-II-1) (AI-1), where a ₁ is a number from 2 to 10, (A-III-2), where a ₃ is a number from 2 to 10, (BI-1) (B-II-1), where b ₁ is a number from 1 to 10. 2. A mixture according to claim 1, comprising compounds of formula (A-I-1) and formula (A-III-2) in combination with a compound of formula (B-I-1). 3. A mixture according to claim 1, comprising compounds of formula (A-I-1) and formula (A-III-2) in combination with a compound of formula (B-II-1).