WO2009095344A1

WO2009095344A1 - Degradable material

Info

Publication number: WO2009095344A1
Application number: PCT/EP2009/050644
Authority: WO
Inventors: Stefano Gardi; Massimiliano Sala; Claudia Pasti
Original assignee: Basf Se; Ciba S.P.A.
Priority date: 2008-01-31
Filing date: 2009-01-21
Publication date: 2009-08-06

Abstract

A composition containing (a) an organic polymer, (b-l) one, two or more compounds of the formula (I) wherein m and n independently are an integer from 2 to 10 x 106; the recurring units X can have the same definition or different definitions, the recurring units Y can have the same definition or different definitions and the recurring units X and Y can have a random distribution or a block distribution; X is a group of the formula (ll-1-a) or (ll-1-b) and Y is a group of the formula (II-2); in which X1, X2, X3, X4 and X5 independently of one another are hydrogen, C1-C4alkyl or phenyl; A1 and A2 independently of one another are -O- 1/r Mr+, -O- N+(R1)4, -O-R2 or -N(R3)2, or A1 and A2 together form the radical -O- or the group -N-O-A0; A3 and A4 independently of one another are -O- 1/r Mr+, -O- N+(R1)4, -O-R2 Or -N(R3)2, or A3 and A4 together form the radical -O- or the group -N-O-A0; M is a metal cation of valency r with r being 1, 2, 3 or 4; R1, R2 and R3 independently of one another are hydrogen, C1-C20alkyl, C3-C12cycloalkyl unsubstituted or substituted by 1, 2 or 3 C1-C4alkyl; C5-C12cycloalkenyl unsubstituted or substituted by 1, 2 or 3 C1-C4alkyl; a bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms; phenyl unsubstituted or substituted by 1, 2 or 3 C1-C4alkyl; or C7-C9phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4alkyl; A0 is for example hydrogen; Y1, Y2, Y3 and Y4 independently of one another a

Description

Degradable material

The present invention relates to a composition having accelerated degradability triggered by light and/or heat and/or humidity and containing an organic polymer, e.g. a natural and/or a synthetic polymer, and a particular degradation accelerator; to an article made of said composition; to the use of the degradation accelerator for controlling the weathering resistance and the degradation of a polymer article; as well as to several novel degradation accelarators.

Plastic articles find widespread applications in everyday life because of their durability in use and cost effectiveness. With proper stabilization, most commercial plastics are made to last for years.

In recent years however, environmental concern has lead to the development of so called biodegradable materials, of diverse origin and nature, which will maintain their function and integrity during service life, but disintegrate after use into carbon dioxide and water, either triggered by chemical means or by microorganisms. One problem however is establishing a suitable equilibrium between biodegradability and integrity during service life.

In more detail, the present invention relates to a composition containing (a) an organic polymer,

(b-l) one, two or more compounds of the formula (I) — (X) (Y) — (I) wherein m and n independently are an integer from 2 to 10 x 10⁶, preferably 40 to 5 x 10⁶; the recurring units X can have the same definition or different definitions, the recurring units Y can have the same definition or different definitions and the recurring units X and Y can have a random distribution or a block distribution or are alternating; X is a group of the formula (ll-1-a) or (ll-1-b) and

Y is a group of the formula (II-2);

in which Xi, X₂, X3, X₄ and X₅ independently of one another are hydrogen, d-C₄alkyl or phenyl;

A₁ and A₂ independently of one another are -O 1/r M^r , -O N (Ri)₄, -0-R₂ or -N(R₃)₂, or A₁ and A₂ together form the radical -O- or the group -N-O-A₀;

A₃ and A₄ independently of one another are -O 1/r M^r , -O N (Ri)₄₁ -O-R₂ Or -N(Ra)₂, or A₃ and A₄ together form the radical -O- or the group -N-O-A₀; M is a metal cation of valency r with r being 1 , 2, 3 or 4;

Ri, R₂ and R₃ independently of one another are hydrogen, Ci-C₂₀alkyl, C₃-Ci₂cycloalkyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl; C₅-Ci₂cycloalkenyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl; a bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms; phenyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl; or C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 Ci-C₄alkyl;

A₀ is hydrogen, Ci-C₃₀alkyl, C₂-C_3oalkenyl, C₃-Ci₂cycloalkyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl; C₅-Ci₂cycloalkenyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl; a bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms, Cr-Cgphenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 Ci-C₄alkyl; diphenylmethyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 CrC₄alkyl; triphenylmethyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 C_rC₄alkyl; C₂-C_3oacyl, -COOE₀, -C_rC₃₀sulfonyl, -Si(Ei)₃ or -Si(OE₂)₃;

E₀, E₁ and E₂ independently of one another are hydrogen, CrCi₈alkyl, C₃-Ci₈alkenyl, C₃-Ci₂cycloalkyl which is unsubstituted or substituted by 1 , 2 or 3 CrC₄alkyl; phenyl which is unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl; or C₇-C₉phenylalkyl which is unsubstituted or substituted on the phenyl by 1 , 2 or 3 Ci-C₄alkyl; Yi, Y₂, Y3 and Y₄ independently of one another are hydrogen, d-C₄alkyl or phenyl; and (b-ll) optionally one, two or more inorganic or organic salts of a transition metal.

According to a preferred embodiment of the present invention, in the formula (I) all recurring units X are indentical, all recurring units Y are identical and the recurring units X and Y can have a random distribution or a block distribution or are alternating.

When X is a group of the formula (11-1 -b) wherein A₃ and A₄ together form a radical -O- , the composition preferably contains component (b-ll).

More general, when X is a group of the formula (ll-1-b), the composition preferably contains the component (b-ll).

A further embodiment of the present invention is a degradation accelerator mixture containing the components (b-l) and (b-ll) as defined above.

The weight ratio of components (b-l)/(b-ll) is preferably 10 000/1 to 1/50 000, more preferably 2 000/1 to 1 /5 000 or 1 /100 to 100/1 or 1 /20 to 20/1.

The compounds of the formula (I) can be prepared according to known methods, for example in analogy to the methods described in the present examples. Several compounds of the formula (I) are commercially available.

The end groups which terminate the polymeric compounds of the formula (I) depend on the preparation; e.g. on the chain termination agents (capping agents) used during the polymerization process. They can also be modified after polymerization.

A suitable example of the end groups is hydrogen. - A -

Examples of alkyl having up to 30 carbon atoms are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3-dimethyl- butyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3- methylheptyl, n-octyl, 2-ethylhexyl, 1 ,1 ,3-trimethylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1 ,1 ,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and eicosyl.

Examples of alkenyl having up to 30 carbon atoms are allyl, 2-methallyl, butenyl, pentenyl, hexenyl and oleyl. The carbon atom in position 1 is preferably saturated. Cβ-Cisalkenyl is particularly preferred.

Examples of C₃-Ci₂cycloalkyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl and 2-methylcyclohexyl. C₅-C₆cycloalkyl unsubstituted or substituted by methyl are preferred.

Examples of C₅-Ci₂cycloalkenyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl are cyclohexenyl and methylcyclohexenyl.

Examples of phenyl substituted by 1 , 2 or 3 CrC₄alkyl are 4-methylphenyl, 2-ethylphenyl, A- ethylphenyl, 4-isopropylphenyl, 4-tert-butyl phenyl, 4-sec-butylphenyl, 4-isobutylphenyl, 3,5-dimethylphenyl, 3,4-dimethylphenyl, 2,4-dimethylphenyl, 2,6-diethylphenyl, 2-ethyl- 6-methylphenyl and 2,6-diisopropylphenyl.

An example of diphenylmethyl substituted on the phenyl by 1 , 2 or 3 CrC₄alkyl is di[methylphenyl]methyl.

An examples of triphenylmethyl substituted on the phenyl by 1 , 2 or 3 Ci-C₄alkyl is tris[methylphenyl]methyl.

Examples of Cr-Cgphenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3

Ci-C₄alkyl are benzyl, 2-phenylethyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl and tert- butylbenzyl. Examples of acyl having up to 30 carbon atoms are C₂-C₃oalkanoyl, C₃-C₃₀alkenoyl and unsubstituted or substituted benzoyl. C₂-C₂oalkanoyl, C₃-C₂oalkenoyl and substituted benzoyl are preferred. Acetyl, propionyl, butyryl, pentanoyl, hexanoyl, octanoyl, benzoyl, acryloyl and crotonoyl are more specific examples.

o

A preferred example of Ci-C₃₀sulfonyl is the group s _E wherein E₃ is Ci-C₃₀alkyl, o

C₃-C₃₀alkenyl, C₃-Ci₂cycloalkyl which is unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl; phenyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₂oalkyl; or C₇-C₉phenylalkyl which is unsubstituted or substituted on the phenyl by 1 , 2 or 3 CrC₄alkyl.

Examples of a bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms are

M is preferably a cation selected from the group consisting of alkali metal cations, earth alkali metal cations and transition metal cations, in particular from the group consisting of the cations of Li, Na, K, Ca, Mg, Mn, Fe, Co, Ni, Cu, V, Zn and Ce.

X is preferably one of the following groups

-CH CH O=_C^ ^CH 1 wherein A₁ and A₂ are equal and are -O^" 1/r M^r+

C=O

A, A₂

(ll-1-a-1 )

1-1 -a-2)

1-1 -b-1 )

CH CH o=c c=o wherein A₃ and A₄ are equal and are -O 1/r M^r .

A₃ A₄

[II-1-D-2)

(II-1-D-3)

The groups (11-1 -a-2) and (ll-i-b-3) are particularly preferred.

The ratio m/n is preferably 1/5000 to 100/50, more preferably 1/2500 to 80/50, in particular 1/1000 to 1/5 or 60/50 to 40/50.

Compounds of the formula (I), wherein X₁, X₂, X3, X₄ and X₅ are hydrogen, A₀ is hydrogen, Ci-C₃oalkyl or C₃-Ci₂cycloalkyl and Yi, Y₂, Y₃ and Y₄ are hydrogen, are preferred.

Compounds of the formula (I), wherein X₁, X₂, X₃, X₄ and X₅ are hydrogen, A₁ and A₂ are -O^"(1/2 Mn²⁺) or together form a radical -O-, A₃ and A₄ are -0^"Na⁺ or together form a group -N-OH and Y₁, Y₂, Y₃ and Y₄ are hydrogen, are particularly preferred.

Of particular interest is a compound of the formula (I) which corresponds to

having a random distribution of the repeating units.

Of further interest is a compound of the formula (I) which corresponds to having an alternating distribution of the repeating units that

means a compound of the formula

wherein x is (m + n)/2 with m and n being equal.

Component (b-ll) is preferably a metal salt of a fatty acid with a carbon number ranging from C₂ to C₃6, in particular from Ci₂ to C₃6- Particularly preferred examples are metal carboxylates of palmitic acid (Ci₆), stearic acid (Ci₈), oleic acid (Ci₈), linoleic acid (Ci₈), linolenic acid (Ci₈) and naphthenic acid. Further examples of component (b-ll) are aromatic acids, e.g. benzoic acid. Component (b-ll) as C₂-C₃₆carboxylate, in particular stearate, palmitate or naphthenate, of Fe, Ce, Co, Cu, V, Mn or Ni is of particular interest.

A further preferred embodiment of the present invention relates to component (b-ll) as a Ci₂-C₂₀alkanoate of Mn, or a Ci₂-C₂₀alkenoate of Mn. Mn-stearate is particularly preferred.

According to another preferred embodiment of the present invention, component (b-ll) contains two different metal salts, in particular with different metal cations, e.g. in a molar ratio of 1 :9 to 9:1.

Examples of component (b-ll) containing two different metal salts are the following mixtures:

11-1 ) Mn-stearate and Fe-stearate,

II-2) Mn-stearate and Co-stearate,

II-3) Mn-stearate and Ce-stearate,

II-4) Co-stearate and Fe-stearate, II-5) Co-stearate and Ce-stearate,

II-6) Ce-stearate and Fe-stearate,

II-7) Mn-palmitate and Fe-palmitate,

II-8) Mn-palmitate and Co-palmitate,

II-9) Mn-palmitate and Ce-palmitate, 11-10) Co-palmitate and Fe-palmitate, 11-1 1 ) Co-palmitate and Ce-palmitate,

11-12) Ce-palmitate and Fe-palmitate,

11-13) Mn-naphthenate and Fe-naphthenate,

11-14) Mn-naphthenate and Co-naphthenate, 11-15) Mn-naphthenate and Ce-naphthenate,

11-16) Co-naphthenate and Fe-naphthenate,

11-17) Co-naphthenate and Ce-naphthenate,

11-18) Ce-naphthenate and Fe-naphthenate,

11-19) Mn-stearate and Mn-palmitate, II-20) Mn-stearate and Fe-palmitate,

11-21 ) Mn-stearate and Co-palmitate,

II-22) Mn-stearate and Ce-palmitate,

II-23) Co-stearate and Fe-palmitate,

II-24) Co-stearate and Ce-palmitate, II-25) Ce-stearate and Fe palmitate,

II-26) Mn-palmitate and Fe-stearate,

II-27) Mn-palmitate and Co stearate,

II-28) Mn palmitate and Ce-stearate,

II-29) Co-palmitate and Fe-stearate, II-30) Co-palmitate and Ce-stearate,

11-31 ) Ce-palmitate and Fe-stearate,

II-32) Mn-naphthenate and Mn-stearate,

II-33) Mn-naphthenate and Fe-stearate,

II-34) Mn-naphthenate and Co-stearate, II-35) Mn-naphthenate and Ce-stearate,

II-36) Co-naphthenate and Fe-stearate,

II-37) Co-naphthenate and Ce-stearate,

II-38) Ce-naphthenate and Fe-stearate.

Further examples of component (b-ll) are manganese titanate, manganese borate^*), manganese potassium sulfate^*), manganese pyrophosphate^*), manganese sulfamate^*), manganese ferrite, manganese(ll) tetraborate, containing calcium carbonate, manganese dioxide, manganese sulfate^*), manganese nitrate^*), manganese chloride^*), and manganese phosphate^*).

^*) in hydrated or non-hydrated form.

In general, the composition may additionally contain one, two or more conventional additives which are either commercially available or can be prepared according to known methods. Examples of said conventional additives are listed below.

1. Antioxidants

1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu- tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethyl- phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth- oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 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 there- of.

1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl- thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4- nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-bu- tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hy- droxyphenyl) adipate.

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

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

1.6. Alkylidenebisphenols, 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'-methylenebis(6-nonyl-4- methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butyl- phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(α-methylben- zyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methy- lenebis(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)dicyclopenta- diene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephtha- late, 1 ,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphe- nyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,

1 ,1 ,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

1.7. Q-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydi- benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, 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-hydroxy- benzyl)sulfide, isooctyl-S.δ-di-tert-butyl^-hydroxybenzylmercaptoacetate. 1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di- dodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1 ,1 ,3,3-te- tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hydroxybenzyl compounds, for example 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame- thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

1.10. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy- anilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1 ,3,5-tri- azine, 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-hydroxyben- zyl)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-hydroxy- phenylpropionyl)-hexahydro-1 ,3,5-triazine, 1 ,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)iso- cyanurate.

1.1 1. Benzylphosphonat.es, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl-δ-tert-butyl^-hydroxy-S-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols, for example 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-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9- nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy- lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hy- droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol- propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.14. Esters of β-(5-tert-butyl-4-hvdroxy-3-methylphenyl)propionic acid with mono- or poly- hydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanedi- ol, 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, trimethyl- olpropane, 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-dicvclohexyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. 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)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1 -phospha^θj-trioxabicyclop^^octane.

1.16. Esters of 3,5-di-tert-butyl-4-hvdroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. 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)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.17. Amides of β-(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert- butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxy- phenylpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hy- drazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Nau- gard^®XL-1 , supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C)

1.19. Aminic antioxidants, for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-bu- tyl-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'-dicy- clohexyl-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'-phe- nyl-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-isopropoxydiphenyl- amine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naph- thylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-butyl- aminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4- octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylamino- methylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetra- methyl-4,4'-diaminodiphenylmethane, 1 ,2-bis[(2-methylphenyl)amino]ethane, 1 ,2-bis(phenyl- amino)propane, (o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N- phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenyl- amines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyl- diphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro- 3,3-dimethyl-4H-1 ,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert- butyl/tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1 ,4-diaminobut-2-ene.

2. UV absorbers and light stabilizers

2.1. 2-(2'-Hvdroxyphenyl)benzotriazoles, for example 2-(2'-hydroxy-5'-methylphenyl)-benzo- triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe- nyl)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'-methylphe- nyl)-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-ethylhexyl- oxy)-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-meth- oxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonyl- ethyl)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-benzotriazole-2-ylphenol]; the transesterification product of 2-[3'-tert-bu- tyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol

300; [R-CH₂CH₂-COO-CH₂CH₂-^- , where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotri-

azol-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]ben- zotriazole.

2.2. 2-Hvdroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl- oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben- zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo- ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxyben- zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphe- nylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinna- mate, butyl α-cyano-β-methyl-p-methoxy-cinnamate, methyl α-carbomethoxy-p-methoxycin- namate, N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline, neopentyl tetra(α-cyano-β,β-di- phenylacrylate.

2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis[4-(1 ,1 ,3,3-tetramethyl- butyl)phenol], such as the 1 :1 or 1 :2 complex, with or without additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert- butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphe- nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands. 2.6. Sterically hindered amines, for example carbonic acid bis(1-undecyloxy-2, 2,6,6- tetramethyl-4-piperidyl)ester, 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, the condensate of 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-di- chloro-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 ,1'-(1 ,2-ethanediyl)-bis(3,3,5,5-tetrame- thylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethyl- piperidine, bis(1 , 2,2,6, 6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)- malonate, 3-n-octyl-7,7,9,9-tetramethyl-1 ,3,8-triazaspiro[4.5]decane-2,4-dione, bis(1-octyl- oxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succi- nate, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene- diamine and 4-morpholino-2,6-dichloro-1 ,3,5-triazine, the condensate 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, the condensate 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-tetrame- thyl-1 ,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1 -(2,2,6, 6-tetramethyl-4-piperidyl)pyr- rolidine-2,5-dione, 3-dodecyl-1-(1 ,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6- dichloro-1 ,3,5-triazine, a 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]); a condensate of 1 ,6-hexanediamine and 2,4, 6-trichloro-1 ,3,5-triazine as well as 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, a reaction product of 7,7,9, θ-tetramethyl^-cycloundecyl-i-oxa-S.δ-diaza^-oxo- spiro-[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, a diester of 4-methoxymethylenemalonic acid with 1 ,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2, 2,6,6- tetramethyl-4-piperidyl)]siloxane, a reaction product of maleic acid anhydride-α-olefin copolymer 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-methylpropoxy)-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, the 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-ami- nopropyl)ethylenediamine), 1 ,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazine-3-one-4- yl)amino)-s-triazine, 1 ,3,5-tris(N-cyclohexyl-N-(1 ,2,2,6,6-pentamethylpiperazine-3-one-4-yl)- amino)-s-triazine.

2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture 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-propyl- oxyphenyl)-6-(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4- methylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2- [2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1 ,3,5-triazine, 2-[2- hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1 ,3,5-triazine, 2-[4- (dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl- phenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1 ,3,5-triazine, 2-(2-hydr- oxy-4-methoxyphenyl)-4,6-diphenyl-1 ,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2- hydroxypropoxy)phenyl]-1 ,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl- 1 ,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4- dimethylphenyl)-1 ,3,5-triazine, 2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4- methoxyphenyl)-1 ,3,5-triazine. 3. Metal deactivators, for example N,N'-diphenyloxamide, 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 bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl- oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, 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, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)- pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristea- ryl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 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'-te- tra-tert-butyl-1 ,1 '-biphenyl-2,2'-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)- 1 ,3,2-dioxaphosphirane.

The following phosphites are especially preferred:

Tris(2,4-di-tert-butylphenyl) phosphite (lrgafos^®168, Ciba Specialty Chemicals Inc.), tris(no- nylphenyl) phosphite,

5. Hydroxylamines, for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N, N- dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N, N- dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydrox- ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.

6. Nitrones, for example, N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl- alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnnitrone, N- hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-al- pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta- decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxyl- amine derived from hydrogenated tallow amine.

7. Thiosynergists, for example dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate or distearyl disulfide.

8. Peroxide scavengers, for example esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β- dodecylmercapto)propionate.

9. Polvamide stabilizers, for example copper salts in combination with iodides and/or phos- phorus compounds and salts of divalent manganese.

10. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.

1 1. Nucleating agents, for example inorganic substances, such as talcum, 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, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). Especially preferred are 1 ,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1 ,3:2,4-di(paramethyl- dibenzylidene)sorbitol, and 1 ,3:2,4-di(benzylidene)sorbitol.

12. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibres, 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, for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.

14. Benzofuranones and indolinones, for example those disclosed 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-431661 1 ; 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-stearoyloxy- ethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)ben- zofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-di- methylphenyl)-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-isooctyl- benzofuran-2-one.

The conventional additive is for example present in the composition in an amount of 0.001 to 10% by weight, preferably 0.001 to 5% by weight, relative to the weight of the organic polymer (component(a)).

A composition, which contains in addition one, two or more of the following components:

(b-lll) a filler or reinforcing agent,

(b-IV) a pigment,

(b-V) a light stabilizer,

(b-VI) a processing additive, (b-VI I) an antioxidant,

(b-VI 11 ) an inorganic or organic salt of Ca, Mg, Zn or Al, or an oxide of Ca, Mg, Zn or Al,

(b-IX) a terpene derivative,

(b-X) an inorganic oxidant,

(b-XI) a compound containing a group o N ^N-O- C

O which is different from component (b-l), (b-XII) an acrylate polymer or copolymer or an acrylate derivative polymer or copolymer, is preferred. Several examples of these components can be found in the above list of conventional additives

Examples of the components (b-lll) to (b-VIII) are disclosed in detail in US-A-2003-0236325 which is incorporated by reference herein.

Component (b-lll) covers e.g. calcium carbonate, silicas, glass fibres, glass bulbs, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour, flours of other natural products, synthetic fibers and metal stearates used as fillers such as calcium stearate or zinc stearate; unsaturated organic polymers such as polybutadiene, polyisoprene, polyoctenamer, or unsaturated acids such as stearic acid, oleic acid, linoleic acid or linolenic acid; and further polymers such as polyethylene oxide or polypropylene oxide.

Component (b-IV) is for example carbon black, titanium dioxide (anatase or rutile which may range in particle size from e.g. 1000 μm to 10 nm and which may optionally be surface treated) or another organic or inorganic colour pigment frequently used in agricultural applications (for example carbon black, brown, silver, red, green).

Component (b-V) is preferably a hindered amine light stabilizer (HALS) or an UV absorber. Examples of preferred hindered amine light stabilizers are also those compounds which are disclosed for example as components (A), (B) and (C) in WO-A-01/92,392 which is incorporated by reference herein and which is equivalent to U.S. Patent Application No. 10/257,339.

Component (b-VI) is for example an antislip/antiblock additive, a plasticizer (e.g. polyglycol), an optical brightener, an antistatic agent, a blowing agent or a process stabilizer.

Component (b-VII) is for example a phenolic antioxidant.

Component (b-VIII) is for example a metal stearate, e.g. calcium stearate or zinc stearate; or zinc oxide (which may range in particle size from e.g. 1000 μm to 10 nm and which may optionally be surface treated). The polyterpene resins used as component (b-IX) may be of natural or synthetic origin. They are either commercially available or can be prepared according to known methods.

The polyterpene resins are for example based on acyclic terpenes or cyclic terpenes, e.g. monocyclic terpenes or bicyclic terpenes. Polyterpenes based on terpene hydrocarbons are preferred.

Examples of acyclic terpenes are terpene hydrocarbons, e.g. myrcene, ocimene and beta-farnesene; terpene alcohols, e.g. dihydromyrcenol (2,6-dimethyl-7-octen-2-ol), geraniol (3,7-dimethyl-trans-2,6-octadien-1-ol), nerol (3,7-dimethyl-cis-2,6-octadien-1-ol), linalool (3,7-dimethyl-1 ,6-octadien-3-ol), myrcenol (2-methyl-6-methylene-7-octen-2-ol), lavandulol, citronellol (3,7-dimethyl-6-octen-1-ol), trans- trans-farnesol (3,7,1 1-trimethyl-2,6,10-dodecatrien-1-ol) and trans-nerolidol (3,7,1 1-trimethyl-

1 ,6,10-dodecatrien-3-ol); terpene aldehydes and acetals, e.g. citral (3,7-dimethyl-2,6-octadien-1-al), citral diethyl acetal (3,7-dimethyl-2,6-octadien-1- aldiethyl acetal), citronellal (3,7-dimethyl-6-octen-1-al), citronellyloxyacetaldehyde and

2,6,10-trimethyl-9-undecenal; terpene ketones, e.g. tagetone, solanone and geranylacetone (6,10-dimethyl-5,9-undecadien-2-one); terpene acids and esters, e.g. cis-geranic acid, citronellic acid, geranyl esters (including geranyl formate, geranyl acetate, geranyl propionate, geranyl isobutyrate and geranyl isovalerate), neryl esters (including neryl acetate), linalyl esters (including linalyl formate, linalyl acetate, linalyl propionate, linalyl butyrate and linalyl isobutyrate), lavandulyl esters (including lavandulyl acetate), citronellyl esters (including citronellyl formate, citronellyl acetate, cintronellyl propionate, citronellyl isobutyrate, citronellyl isovalerate and citronellyl tiglate); and nitrogen containing unsaturated terpene derivatives, e.g. cis-geranic acid nitrile and citronellic acid nitrile.

Examples of cyclic terpenes are cyclic terpene hydrocarbons, e.g. limonene (1 ,8-p-methadiene), alpha-terpinene, gamma-terpinene (1 ,4-p-menthadiene), terpinolene, alpha-phellandrene (1 ,5-p-menthadiene), beta-phellandrene, alpha-pinene (2- pinene), beta-pinene (2(10)-pinene), camphene, 3-carene, caryophyllene, (+)-valencene, thujopsene, alpha-cedrene, beta-cedrene and longifolene; cyclic terpene alcohols and ethers, e.g.

(+)-neoiso-isopulegol, isopulegol (8-p-menten-3-ol), alpha-terpineol (1-p-menten-8-ol), beta- terpineol, gamma-terpineol, delta-terpineol and 1-terpinen-4-ol (1-p-menten-4-ol); cyclic terpene aldehydes and ketones, e.g. carvone (1 ,8-p-mantadien-6-one), alpha-ionone (Ci₃H₂oO), beta-ionone (Ci₃H₂oO), gamma- ionone (Ci₃H₂oO), irone (alpha-, beta-, gamma-) (Ci₄H₂₂O), n-methylionone (alpha-, beta-, gamma-) (Ci₄H₂₂O), isomethylionone (alpha-, beta-, gamma-) (Ci₄H₂₂O), allylionone (Ci₆H₂₄O), pseudoionone, n-methylpseudoionone, isomethylpseudoionone, damascones (1- (2,6,6-trimethylcycohexenyl)-2-buten-1-ones; including beta-damascenone (1 -(2,6,6- trimethyl-1 ,3-cyclohadienyl)-2-buten-1-one)), nootkatone (5,6-dimethyl-8- isopropenylbicyclo[4.4.0]-1-decen-3-one) and cedryl methyl ketone (Ci₇H₂₆O); and cyclic terpene esters, e.g. alpha-terpinyl acetate (1-p-menthen-8-yl acetate), nopyl acetate ((-)-2-(6,6- dimethylbicyclo[3.1.1]hept-2-en-2-yl)ethyl acetate) and khusymil acetate.

Further suitable terpene derivatives can be found in Kirk-Othmer, Encyclopedia of Chemical Technology, John Wiley & Sons, 4. ed. (1994), Vol. 23, p. 833-882.

Preferred examples of terpenes which can serve as the basis for the polyterpenes are tricyclene, alpha-pinene, alpha-fenchene, camphene, beta-pinene, myrcene, cis-pinane, cis/trans-p-8-menthene, trans-2-p-menthene, p-3-menthene, trans-p-menthane, 3-carene, cis-p-menthane, 1 ,4-cineole, 1 ,8-cineole, alpha-terpinene, p-1-menthene, p-4(8)-menthene, limonene, p-cymene, gamma-terpinene, p-3,8-menthadiene, p-2,4(8)-menthadiene and terpinolene.

Further examples of component (b-IX) are cycloaliphatic compounds structurally related to terpenes such as the following alcohols, e.g. 5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-3-methylpentan-2-ol; aldehydes, e.g.

2,4-dimethyl-3-cyclohexene carboxaldehyde, 4-(4-methyl-3-penten-1 -yl)-3-cyclohexene carboxaldehyde and 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene carboxaldehyde; ketones, e.g. civetone, dihydrojasmone (3-methyl-2-pentyl-2-cyclopenten-1-one), cis-jasmone (3-methyl-2- (2-cis-penten-1 -yl)-2-cyclopenten-1 -one), 5-cyclohexadecen-1 -one, 2,3,8,8-tetramethyl- 1 ,2,3,4,5,6,7,8-octahydro-2-napthalenyl methyl ketone and 3-methyl-2-cyclopenten-2-ol-1- one; and esters, e.g.

4,7-methano-3a,4,5,6,7,7a-hexahydro-5-(or 6)-indenyl acetate, allyl 3-cyclohexylpropionate, methyl dihydrojasmonate methyl (3-oxo-2-pentylcyclopentyl) acetate.

The polyterpenes used in the present invention may also be derived from the copolymerisation of the aforementioned terpenes with other unsaturated organic compounds.

Other examples of component (b-IX) are the unsaturated coal-tar by-product polymers such as cumarone-indene resins, rosin and the like.

Present component (b-IX) is preferably a polyterpene resin selected from the group consisting of poly-alpha-pinene, poly-beta-pinene, polylimonene or a copolymer of alpha- pinene, a copolymer of beta-pinene or a copolymer of limonene. Poly-beta-pinene is particularly preferred.

Terpene-based hydrocarbon resins are typically based on products such as alpha-pinene, beta-pinene and d-limonene, which are obtained from the wood and citrus industry, respectively. Terpene-based resins have been available since the mid-1930s (Kirk-Othmer, Encyclopedia of Chemical Technology, John Wiley & Sons, 4. ed. (1994), Vol. 13, p. 717- 718). Polymerization of monoterpenes is most commonly accomplished by carbocationic polymerization utilizing Friedel-Crafts-type catalyst systems, such as aluminum chloride

(Kirk-Othmer, Encyclopedia of Chemical Technology, John Wiley & Sons, 4. ed. (1994), Vol. 1 , p.459). In general, the polyterpenes of the present invention have more than one terpene unit. They have preferably a molecular weight of about 400 g/mol to about 1400 g/mol.

Component (b-X) is in particular an inorganic peroxide or an inorganic superoxide, in particular of an alkali metal or an alkaline earth metal, or of a transition metal. Suitable examples of component (b-X) as a peroxide are magnesium peroxide (MgO₂), calcium peroxide (CaO₂), strontium peroxide (SrO₂), barium peroxide (BaO₂), lithium peroxide (Li₂O₂), sodium peroxide (Na₂O₂), potassium peroxide (K₂O₂), zinc peroxide (ZnO₂), silver peroxide (Ag₂O₂), copper peroxide or iron peroxide. Suitable examples of component (b-X) as a superoxide are lithium superoxide (LiO₂), sodium superoxide (NaO₂), potassium superoxide (KO₂), rubidium superoxide (RbO₂) and cesium superoxide (CsO₂). Preferred are lithium peroxide, sodium peroxide, magnesium peroxide, calcium peroxide, barium peroxide, zinc peroxide and potassium superoxide. Particularly preferred are sodium peroxide, magnesium peroxide, calcium peroxide and zinc peroxide. A comprehensive summary of inorganic peroxides or superoxides, which are useful for the present invention, is given in Kirk-Othmer, Encyclopedia of Chemical Technology, John Wiley & Sons, 4. ed. (1994), Vol. 18, pages 202-229, which is incorporated by reference herein. Blends of the abovementioned peroxides and/or superoxides can also be used.

Component (b-X) is preferably an inorganic peroxide of an alkali metal, an alkaline earth metal or a transition metal, or an inorganic superoxide of an alkali metal, an alkaline earth metal or a transition metal.

Further preferred examples of component (b-X) are magnesium peroxide, calcium peroxide, strontium peroxide, barium peroxide, lithium peroxide, sodium peroxide, potassium peroxide, zinc peroxide, silver peroxide, copper peroxide, iron peroxide, lithium superoxide, sodium superoxide, potassium superoxide, rubidium superoxide and cesium superoxide; in particular sodium peroxide, magnesium peroxide, calcium peroxide and zinc peroxide; especially calcium peroxide.

Component (b-X) is conveniently a compound which - when in contact with humidity - reacts with water in order to liberate an active auxiliary prodegradant species, and which is thermoprocessable in a temperature range between 100° and 300° C. Component (b-XI) is for example the degradation accelerator disclosed in WO-A-07/028,731 which is incorporated by reference herein. Preferred examples are N-trityloxyphthalimide, N-stearoyloxyphthalimide, N-p-toluene-4-sulfonyloxyphthalimide, N-2-(4- dodecylbenzoyl)benzoyloxyphthalimide, N-N'-dihydroxypyromellitic diimide, N, N'-bis[stearoyloxy]pyromellitic diimide, N-stearoyloxy-1 ,8-naphthalimide, N-octyloxy-4- carboxylic acid octyl ester, N-octadecyloxyphthalimide, 1 ,12-bis[4-carboxy-N- hydroxyphthalimide] dodecyl diester, 1 ,12-bis(4-carboxy-N-stearoyloxyphthalimide) dodecyl diester, 1 ,12-bis[4-carboxy-N-tosyloxyphthalimide] dodecyl diester, 1 ,12-bis[4-carboxy-N- benzyloxyphthalimide] dodecyl diester, 1 ,12-bis[4-carboxy-N-isopropyloxyphthalimide] dodecyl diester, N,N -dihydroxy-benzophenonediimide, N,N -distearoyloxy- benzophenonediimide, N-(tert-butyldiphenylsilanyloxy)-phthalimide, carbonic acid 1 ,3-dioxo- 1 ,3-dihydro-isoindol-2-yl ester octadecyl ester and carbonic acid 1 ,3-dioxo-1 ,3-dihydro- isoindol-2-yl ester methyl ester.

Component (X-Il) is for example an acrylate polymer or copolymer or an acrylate derivative polymer or copolymer. Such polymers or copolymers are e.g. disclosed as compound of the formula (I) in WO Patent Application No. EP2007/05,446 which is incorporated by reference herein. Preferred examples are the metal salts of a compound selected from the group consisting of polyacrylic acid, Ci-C₄alkyl acrylate/acrylic acid copolymer, polymethacrylate, Ci-C₄alkyl methacrylate/methacrylic acid copolymer, acrylic acid/methacrylic acid copolymer, ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/CrC₄alkyl acrylate/acrylic acid copolymer and ethylene/Ci-C₄alkyl methacrylate/methacrylic acid copolymer.

Preferred is also a composition according to the present invention which contains as component (b-ll) Mn-stearate or Co-stearate and as component component (b-VIII) Ca-stearate.

Examples of component (a) are:

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, po- lybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:

a) radical polymerisation (normally under high pressure and at elevated temperature).

b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either π- or σ-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, Na and/or Ilia of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1 ), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copo- lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g. ethylene/norbornene like COC), ethylene/1 -olefins copolymers, where the 1 -olefin is generated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vi- nylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1 ) above, for example polypropylene/ethy- lene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene- acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyal- kylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

4. Hydrocarbon resins (for example C₅-Cg) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.

Homopolymers and copolymers from 1.) - 4.) may have any stereostructure including syndio- tactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers including styrene, α-methylstyrene, all isomers of vinyl toluene, especially p-vinyltoluene, all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, and mixtures thereof. Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.

6a. Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/bu- tadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/pro- pylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/sty- rene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propy- lene/styrene.

6b. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6.), especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).

6c. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6a.).

Homopolymers and copolymers may have any stereostructure including syndiotactic, isotac- tic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.

7. Graft copolymers of vinyl aromatic monomers such as styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acry- lonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo- chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from α,β-unsaturated acids and derivatives thereof such as polyacry- lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni- triles, impact-modified with butyl acrylate.

10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.

1 1. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or ace- tals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1 ) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadi- enes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 1 1 , polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly- m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones or lactides, for example polyethylene terephthalate, polybutylene terephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate and polyhydroxybenzoates as well as copolyether esters derived from hydroxyl- terminated polyethers, and also polyesters modified with polycarbonates or MBS. Copolyesters may comprise, for example - but are not limited to - polybutylensuccinate/terephtalate, polybutyleneadipate/terephthalate, polytetramethyleneadipate/terephthalate, polybutylensuccinate/adipate, polybutylensuccinate/carbonate, poly-3-hydroxybutyrate/octanoate copolymer, poly-3- hydroxybutyrate/hexanoate/decanoate terpolymer. Furthermore, aliphatic polyesters may comprise, for example - but are not limited to - the class of poly(hydroxyalkanoates), in particular, poly(propiolactone), poly(butyrolactone), poly(pivalolactone), poly(valerolactone) and poly(caprolactone), polyethylenesuccinate, polypropylenesuccinate, polybutylenesuccinate, polyhexamethylenesuccinate, polyethyleneadipate, polypropyleneadipate, polybutyleneadipate, polyhexamethyleneadipate, polyethyleneoxalate, polypropyleneoxalate, polybutyleneoxalate, polyhexamethyleneoxalate, polyethylenesebacate, polypropylenesebacate, polybutylenesebacate and polylactic acid (PLA) as well as corresponding polyesters modified with polycarbonates or MBS. The term "polylactic acid (PLA)" designates a homo-polymer of preferably poly-L-lactide and any of its blends or alloys with other polymers; a co-polymer of lactic acid or lactide with other monomers, such as hydroxy-carboxylic acids, like for example, glycolic acid, 3-hydroxy- butyric acid, 4-hydroxy-butyric acid, 4-hydroxy-valeric acid, 5-hydroxy-valeric acid, 6- hydroxy-caproic acid and cyclic forms thereof; the terms "lactic acid" or "lactide" include L- lactic acid, D-lactic acid, mixtures and dimers thereof, i.e. L-lactide, D-lactide, meso-lacide and any mixtures thereof.

19. Polycarbonates and polyester carbonates.

20. Polyketones.

21. Polysulfones, polyether sulfones and polyether ketones.

22. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.

23. Drying and non-drying alkyd resins.

24. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.

25. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acry- lates, urethane acrylates or polyester acrylates.

26. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.

28. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.

29. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, PoIy- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

30. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.

31. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carbo- xylated styrene/butadiene copolymers.

Component (a) is preferably a thermoplastic natural or synthetic polymer. Preferred examples are a) Homo and copolymers of olefin monomers such as ethylene and propylene, but also higher 1 -olefins such as 1-butene, 1-pentene, 1-hexene or 1-octen. Preferred is polyethylene LDPE and LLDPE, HDPE and polypropylene. b) Homo- and copolymers of olefin monomers with diolefin monomers such as butadiene, isoprene and cyclic olefins such as norbornene. c) Copolymers of one ore more 1 -olefins and /or diolefins with carbon monoxide and/or with other vinyl monomers, including, but not limited to, acrylic acid and its corresponding acrylic esters, methacrylic acid and its corresponding esters, vinyl acetate, vinyl ketone, styrene, maleic acid anhydride and vinyl chloride. d) Polyvinyl alcohol e) Other thermoplastics such as poly(meth)acrylate esters, polystyrene, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinylbutyral, ethylene-vinyl alcohol copolymer, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), liquid crystal polyesters (LCPs), polyacetals (e.g., POM), polyamides (PA), polycarbonates, polyurethane and polyphenylene sulfide (PPS); polymer blends or polymer alloys formed of two or more of these resins; and compounds obtained by adding fillers such as glass fibers, carbon fibers, semi-carbonized fibers, cellulose fibers and glass beads, flame retardants, blowing agents, antimicrobial agents, crosslinking agents, fine polyolefin resin powder, polyolefin waxes, ethylene bisamide waxes, metallic soaps and the like either singly or in combination to these resins. Examples of thermosetting resins, on the other hand, can include thermosetting resins such as epoxy resins, melamine resins and unsaturated polyester resins; and compounds obtained by incorporating fillers such as glass fibers, carbon fibers, semi-carbonized fibers, cellulose fibers and glass beads, flame retardants and the like either singly or in combination to these resins.

Further preferred examples of component (a) are polyethylensuccinate, polybutylensuccinate, polybutylensuccinate/adipate, polybutylensuccinate/carbonate, polybutylensuccinate/terephtalate, polycaprolactone, poly(hydroxyalcanoates), poly 3-hydroxybutyrate, polylactic acid, polyester amides, or blends of these materials with natural or modified starch, polysaccarides, lignin, wood flour, cellulose and chitin.

According to a particular preferred embodiment of the present invention component (a) is a polyolefin homo- or copolymer, a starch modified polyolefin or a starch based polymer composite.

According to a further preferred embodiment of the present invention component (a) is polyethylene, polypropylene, a polyethylene copolymer or a polypropylene copolymer.

Component (b-l) is preferably present in the organic polymer (= component (a)) in an amount of 0.001 to 5% by weight or 0.005 to 5% by weight, in particular 0.1 to 3% by weight, relative to the weight of the organic polymer. Component (b-ll) is preferably present in the organic polymer (= component (a)) in an amount of 0.005 to 50% by weight or 0.005 to 10% by weight, in particular 0.005 to 5% by weight, relative to the weight of the organic polymer.

Component (b-lll) is preferably present in the organic polymer (= component (a)) in an amount of 0.05 to 80% by weight, in particular 0.5 to 70% by weight, relative to the weight of the organic polymer.

Component (b-IV) is preferably present in the organic polymer (= component (a)) in an amount of 0.05 to 40% by weight, in particular 0.5 to 30% by weight, relative to the weight of the organic polymer.

Component (b-V) is preferably present in the organic polymer (= component (a)) in an amount of 0.01 to 20% by weight, in particular 0.01 to 10% by weight, relative to the weight of the organic polymer.

Component (b-VI) is preferably present in the organic polymer (= component (a)) in an amount of 0.05 to 10% by weight, in particular 0.05 to 5% by weight, relative to the weight of the organic polymer.

Component (b-VII) is preferably present in the organic polymer (= component (a)) in an amount of 0.001 to 4% by weight, e.g. 0.005 to 1% by weight, in particular 0.01 to 0.3% by weight, relative to the weight of the organic polymer.

Component (b-VIII) is preferably present in the organic polymer (= component (a)) in an amount of 0.005 to 5% by weight, in particular 0.05 to 1% by weight, relative to the weight of the organic polymer.

Component (b-IX) is preferably present in the organic polymer (= component (a)) in an amount of 0.01 to 10% by weight, in particular 0.01 to 5% by weight, relative to the weight of the organic polymer. Component (b-X) is preferably present in the organic polymer (= component (a)) in an amount of 0.005 to 20 % by weight, in particular 0.1 to 15 % by weight, relative to the weight of the organic polymer.

Component (b-XI) is preferably present in the organic polymer (= component (a)) in an amount of 0.01 to 10 % by weight or 0.01 to 5 % by weight, relative to the weight of the organic polymer.

Component (b-XI I) is preferably present in the organic polymer (= component (a)) in an amount of 0.001 to 5% by weight or 0.005 to 5% by weight, in particular 0.1 to 3% by weight, relative to the weight of the organic polymer.

The components (b-l) and optionally (b-ll) to (b-XII) can be incorporated into the organic polymer (= component (a)) in a controlled form by known methods, for example before or during shaping or by applying the dissolved or dispersed compounds to the organic polymer, if necessary with subsequent evaporation of the solvent. The components can be added to the organic polymer in the form of a powder, granules or a masterbatch, which contains these components in, for example, a concentration of from 2.5 to 25 % by weight.

If desired, the components (b-l) and optionally (b-ll) to (b-XII) can be blended with each other before incorporation into the organic polymer (= component (a)). They can be added to the organic polymer before or during the polymerization or before the crosslinking.

The present invention is especially useful in all areas where degradation in humid environments is desired. The use of the present additive mixture can be tailored according to the climatic conditions of the place where an article made of the above described composition will be finally stored for degradation.

A further embodiment of the present invention relates to an article made of a composition as defined above. A brief description of some exemplary articles made in accordance with the invention follows. Typically, the articles are required to have a relatively long service life followed by a relatively short period during which embrittlement and fragmentation occurs, either in situ or in a landfill. The articles may be film products comprising polyolefins or other organic polymers.

Examples of suitable agricultural articles are mulch films, small tunnel films, banana bags, direct covers, nonwoven, twines, clips, nettings, pipes, tubes and pots.

Mulch films represent a particular preferred embodiment of the present invention.

Mulch films are used to protect crops in the early stages of their development. Mulch films, depending on the type of crop and on the purpose, can be laid after the seeding or at the same time as the seeding. They protect the crop until the crop has reached a certain development stage. When the harvest is finished, the field is prepared for another cultivation.

Standard plastic films have to be collected and disposed in order to allow the new cultivation. The additive systems of the present invention (components (b-l) and optionally (b-ll) to (b-XII)), when added to the standard plastic mulch films, allow the film to keep its properties until the crop has reached the required development, then degradation starts and the film is completely embrittled when the new cultivation has to be started.

The length of the service period and of the time to degradation and time to complete disappearance depends on the type of crop and on the environmental conditions. Depending on the specific time requirements, the additive combinations are designed.

By appropriately dosing the amount of the present additive system, the required service periods and time to degradation and disappearance can be obtained. Examples of typical life times of mulch films are 10 to 180 days, lifes up to 24 months can also be required and achieved.

Thus, a further preferred embodiment of the present invention is a mulch film containing the the components (b-l) and optionally (b-ll) to (b-XII) as defined above and having a life time of 10 to 720 days. Mulch films can be mono or multilayer (preferably three layers), transparent or appropriately pigmented (white, black, silver, green, brown) on the base of the agronomic needs.

The thickness of the mulch films can range, for example, between 5 to 100 microns. Films from 10 to 60 microns are preferred. Blown films are particularly preferred. The films may be partly burried with soil.

A particularly preferred embodiment of the present invention is a mulch film made of a composition containing (a) a polyethylene

(b-l) a compound of the formula and optionally

(b-l I) Mn stearate.

Examples of particularly preferred embodiments of the present invention relate to degradable mulch films with the following characteristics:

1) Transparent 10 to 25 micron monolayer or three-layer blown film containing: (a) linear low density polyethylene, (b-l) 0.1 to 1 %, in particular 0.4 %, of a compound of the formula '

(b-ll) 0.05 to 2 %, in particular 0.14 %, of manganese(ll) stearate, (b-lll) 0.1 to 5%, in particular 0.4%, of calcium stearate, (b-V) 0.05 to 2 %, in particular 0.1 %, of Tinuvin 783 (RTM)¹⁾, (b-VI-1) 0.00005 to 0.0005 %, in particular 0.0001 to 0.0002 %, Of SiO₂, (b-VI-2) 0.05 to 4 %, in particular 0.1 to 0.5 %, of tris(2,4-di-t-butylphenyl) phosphite, and (b-VII) 0.001 to 4 %, in particular 0.02 to 2 %, of octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate. 2) Transparent 10 to 25 micron monolayer or three-layer blown film containing: (a) linear low density polyethylene,

(b-l) 0.1 to 1 %, in particular 0.4 %, of a compound of the formula ,

(b-ll) 0.05 to 2 %, in particular 0.14 %, of manganese(ll) stearate, (b-lll) 0.1 to 5%, in particular 0.4%, of calcium stearate,

(b-VI-1) 0.00005 to 0.0005 %, in particular 0.0001 to 0.0002 %, Of SiO₂, (b-VI-2) 0.05 to 4 %, in particular 0.1 to 0.5 %, of tris(2,4-di-t-butylphenyl) phosphite, and (b-VII) 0.001 to 4 %, in particular 0.02 to 2 %, of octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate.

3) Non-transparent 10 to 25 micron monolayer or three-layer blown film: (a) linear low density polyethylene,

(b-l) 0.1 to 1 %, in particular 0.4 %, of a compound of the formula

(b-ll) 0.05 to 2 %, in particular 0.14 %, of manganese(ll) stearate, (b-IV) 0.1 to 20 %, in particular 0.1 to 10 %, of carbon black,

(b-V) 0.1 to 2 %, in particular 0.4 to 1 %, of Tinuvin 783 (RTM)¹⁾,

(b-VI-1) 0.00005 to 0.0005 %, in particular 0.0001 to 0.0002 %, Of SiO₂,

(b-VI-2) 0.05 to 4 %, in particular 0.1 to 0.5 %, of tris(2,4-di-t-butylphenyl) phosphite,

(b-VII) 0.001 to 4 %, in particular 0.02 to 2 %, of octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate.

4) Non-transparent 10 to 25 micron monolayer or three-layer blown film: (a) linear low density polyethylene,

(b-l) 0.1 to 1 %, in particular 0.4 %, of a compound of the formula '

(b-ll) 0.05 to 2 %, in particular 0.14 %, of manganese(ll) stearate, (b-IV) 0.1 to 20 %, in particular 0.1 to 10 %, of carbon black, (b-V) 0.1 to 2 %, in particular 0.4 to 1 %, of Chimassorb 944 (RTM)²⁾, (b-VI-1) 0.00005 to 0.0005 %, in particular 0.0001 to 0.0002 %, Of SiO₂, (b-VI-2) 0.05 to 4 %, in particular 0.1 to 0.5 %, of tris(2,4-di-t-butylphenyl) phosphite, (b-VII) 0.001 to 4 %, in particular 0.02 to 2 %, of octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate.

5) Non-transparent 10 to 25 micron monolayer or three-layer blown film: (a) linear low density polyethylene,

(b-l) 0.1 to 1 %, in particular 0.4 %, of a compound of the formula

(b-ll) 0.05 to 2 %, in particular 0.14 %, of manganese(ll) stearate, (b-IV) 0.1 to 20 %, in particular 0.1 to 10 %, of carbon black, (b-V) 0.1 to 2 %, in particular 0.4 to 1 %, of a light stabilizer LS³⁾, (b-VI-1) 0.00005 to 0.0005 %, in particular 0.0001 to 0.0002 %, Of SiO₂, (b-VI-2) 0.05 to 4 %, in particular 0.1 to 0.5 %, of tris(2,4-di-t-butylphenyl) phosphite, (b-VII) 0.001 to 4 %, in particular 0.02 to 2 %, of octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate.

6) Non-transparent 10 to 25 micron monolayer or three-layer blown film: (a) linear low density polyethylene, (b-l) 0.1 to 1 %, in particular 0.4 %, of a compound of the formula

(b-ll) 0.05 to 2 %, in particular 0.14 %, of manganese(ll) stearate, (b-IV) 0.1 to 20 %, in particular 0.1 to 10 %, of carbon black, (b-VI-1) 0.00005 to 0.0005 %, in particular 0.0001 to 0.0002 %, Of SiO₂, (b-VI-2) 0.05 to 4 %, in particular 0.1 to 0.5 %, of tris(2,4-di-t-butylphenyl) phosphite, (b-VII) 0.001 to 4 %, in particular 0.02 to 2 %, of octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate.

7) Transparent 10 to 25 micron monolayer or three-layer blown film containing: (a) linear low density polyethylene, (b-l) 0.1 to 5 %, in particular 1.6 %, of a compound of the formula ,

(b-ll) 0.05 to 2 %, in particular 0.14 %, of manganese(ll) stearate, (b-V) 0.05 to 2 %, in particular 0.1 %, of Tinuvin 783 (RTM)¹⁾, (b-VI-1) 0.00005 to 0.0005 %, in particular 0.0001 to 0.0002 %, of SiO₂, (b-VI-2) 0.05 to 4 %, in particular 0.1 to 0.5 %, of tris(2,4-di-t-butylphenyl) phosphite, and (b-VII) 0.001 to 4 %, in particular 0.02 to 2 %, of octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate.

8) Transparent 10 to 25 micron monolayer or three-layer blown film containing: (a) linear low density polyethylene,

(b-l) 0.1 to 5 %, in particular 1.6 %, of a compound of the formula ,

(b-ll) 0.05 to 2 %, in particular 0.14 %, of manganese(ll) stearate, (b-VI-1) 0.00005 to 0.0005 %, in particular 0.0001 to 0.0002 %, Of SiO₂, (b-VI-2) 0.05 to 4 %, in particular 0.1 to 0.5 %, of tris(2,4-di-t-butylphenyl) phosphite, and (b-VII) 0.001 to 4 %, in particular 0.02 to 2 %, of octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate.

9) Non-transparent 10 to 25 micron monolayer or three-layer blown film: (a) linear low density polyethylene, (b-l) 0.1 to 5%, in particular 1.6 %, of a compound of the formula '

(b-ll) 0.05 to 2 %, in particular 0.14 %, of manganese(ll) stearate, (b-IV) 0.1 to 20 %, in particular 0.1 to 10 %, of carbon black, (b-V) 0.1 to 2 %, in particular 0.4 to 1 %, of Tinuvin 783 (RTM)¹⁾, (b-VI-1) 0.00005 to 0.0005 %, in particular 0.0001 to 0.0002 %, Of SiO₂, (b-VI-2) 0.05 to 4 %, in particular 0.1 to 0.5 %, of tris(2,4-di-t-butylphenyl) phosphite, (b-VII) 0.001 to 4 %, in particular 0.02 to 2 %, of octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate.

10) Non-transparent 10 to 25 micron monolayer or three-layer blown film: (a) linear low density polyethylene,

(b-l) 0.1 to 5%, in particular 1.6 %, of a compound of the formula ,

(b-ll) 0.05 to 2 %, in particular 0.14 %, of manganese(ll) stearate, (b-IV) 0.1 to 20 %, in particular 0.1 to 10 %, of carbon black, (b-V) 0.1 to 2 %, in particular 0.4 to 1 %, of Chimassorb 944 (RTM)²⁾, (b-VI-1 ) 0.00005 to 0.0005 %, in particular 0.0001 to 0.0002 %, of SiO₂,

(b-VI-2) 0.05 to 4 %, in particular 0.1 to 0.5 %, of tris(2,4-di-t-butylphenyl) phosphite, (b-VII) 0.001 to 4 %, in particular 0.02 to 2 %, of octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate.

11) Non-transparent 10 to 25 micron monolayer or three-layer blown film: (a) linear low density polyethylene,

(b-l) 0.1 to 5%, in particular 1.6 %, of a compound of the formula

(b-ll) 0.05 to 2 %, in particular 0.14 %, of manganese(ll) stearate,

(b-IV) 0.1 to 20 %, in particular 0.1 to 10 %, of carbon black, (b-V) 0.1 to 2 %, in particular 0.4 to 1 %, of a light stabilizer LS³⁾,

(b-VI-1) 0.00005 to 0.0005 %, in particular 0.0001 to 0.0002 %, Of SiO₂,

12) Non-transparent 10 to 25 micron monolayer or three-layer blown film:

(a) linear low density polyethylene, (b-l) 0.1 to 5%, in particular 1.6 %, of a compound of the formula ,

In the above listed preferred embodiments "%" means "% by weight, relative to the weight of the linear low density polyethylene (=component (a))".

The carbon black is preferably added in the form of a masterbatch, e.g. PLASBLAK PE 2642 MB 40% LD (RTM)).

¹⁾ Tinuvin (RTM) 783:

Mixture of poly[[6-[(1 ,1 ,3,3-tetramethylbutyl)amino]-1 ,3,5-triazine-2,4-diyl][(2,2,6,6- tetramethyl-4-piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]] and 1-(2- hydroxyethyl^^θ.θ-tetramethyM-hydroxypiperidine-succinic acid copolymer.

²⁾ Chimassorb (RTM) 944:

Poly[[6-[(1 ,1 ,3,3-tetramethylbutyl)amino]-1 ,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4- piperidyl)imino]hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]].

³⁾ Light stabilizer LS:

Examples of further suitable articles are a packaging material, preferably for consumer products such as food, beverage or cosmetics; a hygienic article and a medical article.

Further examples of articles according to the present invention are geotextiles, landfill covers, industrial covers, waste covers, temporary scaffolding sheets, building films, silt fences, films for building temporary shelter constructions, disposable diapers, disposable garments, and the like.

According to a particularly preferred embodiment, the article is a packaging material such as a supermarket bag or a refuse sack.

When the article according to the present invention is useful for the construction area, it may be for example a geomembrane, a geotextile, a geogrid or a scaffolding film.

The article may be selected from the group consisting of films, fibers, profiles, bottles, tanks, containers, sheets, bags, styrofoam cups, plates, blister packages, boxes, package wrappings and tapes.

The article can be shaped, for example, by injection-molding, blow-molding, compression- molding, roto-molding, slush-molding, extrusion, film casting, film blowing, calendering, thermoforming, spinning or rotational casting. In all of the foregoing examples, the article, made in accordance with the invention, will keep its properties during use and will degrade after its service life.

A further embodiment of the present invention relates to a method for controlling the weathering resistance and the degradation of an organic polymer, which method comprises incorporating into the organic polymer the components (b-l) and optionally (b-ll) to (b-XII) as defined herein.

Some compounds of the formula (I) are novel. Thus, another embodiment of the present invention are the novel compounds of the formula

wherein m and n independently are an integer from 2 to 10 x 10⁶, and the recurring units have a random distribution or a block distribution or the two monomer units are alternating.

The examples below illustrate the invention in greater detail. All percentages and parts are by weight, unless stated otherwise.

Example 1 : Synthesis of ethylene-N-hydroxymaleimide copolymer with alternating monomer units.

(Chemical Abstracts Registry No. 27324-81-8)

Starting from poly(ethylene-alt-maleic anhydride) (available from Aldrich (RTM); 188050), the desired copolymer can be prepared as described in Example 1 of US-A-3,578,641. IR spectrum (ATR): 3449 cm^"1, 3180 cm^"1, 2917 cm^"1, 2849 cm^"1, 1779 cm^"1, 1686 cm^"1, 1465 cm^"1, 1213 cm^"1 , 1046 cm^"1, 719 cm^"1.

Elemental Analysis: Found C, 51.68%; H, 5.39%; N, 9.31%.

Melting range: 168-184°C

Example 2: Synthesis of the disodium salt of ethylene-maleic acid with alternating monomer units.

(Chemical Abstracts Registry No. 9019-23-2)

A four-necked round-bottom flask equipped with a mechanical stirrer, thermocouple, dropping funnel and condenser is successively charged with 10.0 g of polyethylene-alt- maleic anhydride (available from Aldrich (RTM); 188050), 6.3 g of NaOH and 150 ml of a 1 :1 tetrahydrofuran/HOCH₃ solution. Then, the reaction mixture is maintained at reflux temperature for 6 hours. The reaction is cooled at room temperature and the insoluble product is recovered by filtering off the solution and exsiccated in oven under reduced pressure. The desired product is obtained as white solid with a melting point higher than 300⁰C.

IR spectrum (ATR): 3309 cm^"1 , 2940 cm^"1 , 1555 cm^"1 1446 cm^"1 , 1407 cm^"1 , 1072 cm^"1 , 881 cm^"1, 766 cm^"1.

Example 3: Synthesis of the manganese salt of polyethylene graft maleic acid. with random distribution of the repeating units.

n/m molar ratio: 145

A four-necked round-bottom flask equipped with a mechanical stirrer, thermocouple, dropping funnel and condenser is successively charged with 10.0 g of polyethylene-graft- maleic anhydride 3% (Aldrich (RTM); 456632) and 150 ml of tetrahydrofuran. Then, the mixture is heated to reflux temperature and, when it is completely homogeneous, 0.19 g of NaOH in 2 ml of water is dropped to the solution letting to react for 15 minutes. 0.3 g of manganese dichloride in 3 ml of water is dropped to the reaction mixture maintained under stirring at reflux temperature. After 1 hour, 100 ml of water are charged to the reaction at 40⁰C. The insoluble product is then isolated filtering off the solution and exsiccated in oven under reduced pressure. The desired product is obtained as white solid.

Manganese amount by elemental analysis ICP (Inductively Coupled Plasma Spectroscopy): 1.07% (83% of the theory).

IR spectrum (ATR): 2916 cm^"1, 2849 cm^"1, 1711 cm^"1, 1560 cm^"1 , 1471 cm^"1, 1463 cm^"1, 885 cm^"1, 729 cm^"1, 718 cm^"1.

Elemental Analysis: Found C, 82.21%; H, 13.60%; N, 0.77%.

Example 4: Compound of the formula

with random distribution of the repeating units.

n/m molar ratio: 441 The above shown compound can be prepared by reactive extrusion in analogy to the method described in KR-A-2000/006,774 and is also commercially available as FUSABOND E MB226D (RTM).

IR spectrum (ATR): 2915 cm^'1, 2848 cm^'1. 1711 cm^"1, 1471 cm^"1, 718 cm^"1.

Elemental Analysis: Found C, 84.62%; H, 13.87%; N, 0.34%.

Tm (DSC, at peak): 116.5°C.

Example 5: Compound of the formula

with random distribution of the repeating units

n/m molar ratio: 145

The above shown compound can be prepared by reactive extrusion in analogy to the method described in KR-A-2000/006,774 and is also commercially available from Aldrich (RTM) under No. 456,632.

IR spectrum (ATR): 2916 cm^"1, 2848 cm^"1, 1712 cm^"1, 1471 cm^"1, 1463 cm^"1, 1377 cm^"1, 729 cm^"1, 719 cm^"1.

Elemental Analysis: Found C, 83.35%; H, 12.56%.

Tm (DSC, at peak): 100.2⁰C.

Example A:

I) Film manufacture: In a turbo mixer (Caccia (RTM), Labo 10) 5 weight %, relative to the weight of linear low density polyethylene (LLDPE), of manganese stearate is mixed with LLDPE Dowlex (RTM) NG 5056-G which contains 0.10 % by weight of tris(2,4-di-t-butylphenyl) phosphite and 0.032 % by weight of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and which has a melt index of 1.1 g/10 min. (190⁰C / 2.16 Kg). The mixture is extruded at a maximum temperature of 200⁰C using an O. M. C. twin-screw extruder (model ebv 19/25) to granules, which are subsequently diluted with the same LLDPE and optionally with 2 weight % of FUSABOND E MB226D (RTM) in order to obtain the final composition which is converted to a film 12 μm thick, using a blow-extruder (Dolci (RTM)) working at a maximum temperature of 210°C. Table 1 illustrates the final composition of the LLDPE films.

I able 1 :

Film 1 Reference (contains no manganese stearate and no FUSABOND E MB226D (RTM)

Film 2 0.14% of manganese stearate

Film 3 0.14% of manganese stearate + 2% of FUSABOND E MB226D (RTM)

("%" means "% by weight" relative to the LLDPE)

II) Exposure:

1 ) The obtained film samples are exposed in an ATLAS (RTM) Weatherometer (model Ci65A) equipped with a 6500W Xenon lamp (continuous light cycle, black panel temperature = 63 ⁰C).

2) Films are also exposed in a static oven (Heraeus (RTM), model 6120 UT) running at 50⁰C.

III) Evaluation parameters: a) Carbonyl increment (CO): Evaluation of the carbonyl band increment (1710 cm-1 ) in function of the exposure time is monitored with a FT-IR Perkin-Elmer (RTM) Spectrum One. b) Time to cracking: Visual failure of film samples is assessed according to time to the first evidence of surface cracking.

Tables 2 to 5 illustrate the results of carbonyl increment or time to cracking.

Table 2: Carbonyl increment in WOM exposure (in hours) of 12 microns LLDPE films.

Table 3:

Time to cracking in WOM exposure (in hours) of 12 microns LLDPE films.

Table 4:

Carbonyl increment in oven 50⁰C exposure (in hours) of 12 microns LLDPE films.

Table 5:

Time to cracking in oven 50⁰C exposure (in hours) of 12 microns LLDPE films.

Example B:

I) Film manufacture:

In a turbo mixer (Caccia (RTM), Labo 10) 5 weight %, relative to the weight of the LLDPE, of manganese stearate is mixed with LLDPE Dowlex (RTM) NG 5056-E which contains 0.12 % by weight of tris(2,4-di-t-butylphenyl) phosphite, 0.02 % by weight of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and 0.03 % by weight of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and which has a melt index of 1.1 g/10 min. (190°C / 2.16 Kg). The mixture is extruded at a maximum temperature of 200⁰C using an O. M. C. twin-screw extruder (model ebv 19/25). 24 weight % of granules of FUSABOND E MB226D (RTM) and 2.8 weight % of the above mentioned manganese stearate masterbatch are diluted with LLDPE Dowlex (RTM) NG 5056-E which contains 0.12 % by weight of tris(2,4-di-t-butylphenyl) phosphite, 0.02 % by weight of pentaerythritol tetrakis[3-(3,5-di-tert- butyl-4-hydroxyphenyl)propionate and 0.03 % by weight of octadecyl-3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate, and which has a melt index of 1.1 g/10 min. (190⁰C / 2.16 Kg) in order to obtain the final composition which is converted to a film 25 μm thick, using a blow- extruder (Dolci (RTM)) working at a maximum temperature of 210⁰C.

Table 6 illustrates the final composition of the LLDPE films.

Table 6:

Final composition of the LLDPE films.

Film 4 Reference (contains no FUSABOND E MB226D (RTM))

Film 5 24% of FUSABOND E MB226D (RTM) + 0.14 % of manganese stearate ("%" means "% by weight" relative to the LLDPE)

II) Exposure:

2) Films are also exposed in a static oven (Heraeus (RTM), model 6120 UT) running at 50 °C.

Ill) Evaluation parameters: a) Carbonyl increment (CO): Evaluation of the carbonyl band increment (1710 cm-1 ) in function of the exposure time is monitored with a FT-IR Perkin-Elmer (RTM) Spectrum One. b) Time to cracking: Visual failure of film samples is assessed according to time to the first evidence of surface cracking.

Tables 7 and 8 illustrate the results of carbonyl increment or time to cracking.

Table 7:

Carbonyl increment in WOM exposure (in hours) of 25 microns LLDPE films.

Table 8:

Time to cracking in WOM exposure (in hours) of 25 microns LLDPE films.

Claims

Claims:

1. A composition containing

(a) an organic polymer,

(b-l) one, two or more compounds of the formula (I)

-(X) m ^"(^Y> n- (I) wherein m and n independently are an integer from 2 to 10 x 10⁶; the recurring units X can have the same definition or different definitions, the recurring units Y can have the same definition or different definitions and the recurring units X and Y can have a random distribution or a block distribution or are alternating;

X is a group of the formula (ll-1-a) or (ll-1-b) and

Y is a group of the formula (II-2);

in which

Xi, X₂, Xβ, X₄ and X₅ independently of one another are hydrogen, d-C₄alkyl or phenyl;

A₃ and A₄ independently of one another are -O 1/r M^r , -O N (Ri)₄, -0-R₂ or -N(R₃)₂, or A₃ and A₄ together form the radical -O- or the group -N-O-A₀;

M is a metal cation of valency r with r being 1 , 2, 3 or 4;

Ri, R₂ and R₃ independently of one another are hydrogen, Ci-C₂₀alkyl, C₃-Ci₂cycloalkyl unsubstituted or substituted by 1 , 2 or 3 OC₄alkyl; C₅-Ci₂cycloalkenyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl; a bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms; phenyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl; or C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 Ci-C₄alkyl;

A₀ is hydrogen, d-C₃oalkyl, C₂-C₃oalkenyl, C₃-Ci₂cycloalkyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl; C₅-Ci₂cycloalkenyl unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl; a bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms, C₇-C₉phenylalkyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 CrC₄alkyl; diphenylmethyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 Ci-C₄alkyl; triphenylmethyl unsubstituted or substituted on the phenyl by 1 , 2 or 3 C_rC₄alkyl; C₂-C₃₀acyl, -COOE₀, -C_rC₃₀sulfonyl, -Si(Ei)₃ or -Si(OE₂)₃;

E₀, E₁ and E₂ independently of one another are hydrogen, CrCi₈alkyl, C₃-Ci₈alkenyl, C₃-Ci₂cycloalkyl which is unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl; phenyl which is unsubstituted or substituted by 1 , 2 or 3 Ci-C₄alkyl; or C₇-C₉phenylalkyl which is unsubstituted or substituted on the phenyl by 1 , 2 or 3 Ci-C₄alkyl; Yi, Y₂, Y₃ and Y₄ independently of one another are hydrogen, Ci-C₄alkyl or phenyl; and (b-ll) optionally one, two or more inorganic or organic salts of a transition metal.

2. A composition according to claim 1 containing (b-ll) optionally an organic salt of a transition metal.

3. A composition according to claim 1 with the proviso that when X is a group of the formula (ll-1-b) wherein A₃ and A₄ together form a radical -O- , the composition contains component (b-ll).

4. A composition according to claim 1 , wherein in the formula (I) all recurring units X are indentical, all recurring units Y are identical and the recurring units X and Y can have a random distribution or a block distribution or are alternating.

5. A composition according to claim 1 wherein

Xi, X2, Xβ, X₄ and X₅ are hydrogen,

A₀ is hydrogen, Ci-C₃₀alkyl or C₃-Ci₂cycloalkyl, and

Yi, Y2, Y3 and Y₄ are hydrogen.

6. A composition according to claim 1 wherein Xi, X2, Xβ, X₄ and X₅ are hydrogen;

A₁ and A₂ are -O^"(1/2 Mn²⁺) or together form a radical -O-; A₃ and A₄ are -0^"Na⁺ or together form a group -N-OH; and Yi, Y2, Y3 and Y₄ are hydrogen.

7. A composition according to claim 1 wherein component (b-l) is a compound of the formula (I) which corresponds to

8. A composition according to claim 1 wherein the metal cation of component (b-l) is selected from the group consisting of alkali metal cations, earth alkali metal cations and transition metal cations.

9. A composition according to claim 1 wherein the metal cation of component (b-l) is selected from the group consisting of the cations of Li, Na, K, Ca, Mg, Mn, Fe, Co, Ni, Cu, V, Zn and Ce.

10. A composition according to claim 1 containing components (b-l) and (b-ll), wherein component (b-ll) is a C₂-C₃6carboxylate of Fe, Ce, Co, Mn, Cu, V or Ni.

11. A composition according to claim 1 containing components (b-l) and (b-ll), wherein component (b-ll) is a Ci₂-C₂oalkanoate of Mn or a Ci₂-C₂oalkenoate of Mn.

12. A composition according to claim 1 , which contains in addition one, two or more of the following components

(b-lll) a filler or reinforcing agent,

(b-IV) a pigment, (b-V) a light stabilizer,

(b-VI) a processing additive, (b-VII) an antioxidant,

(b-VIII) an inorganic or organic salt of Ca, Mg, Zn or Al, or an oxide of Ca, Mg, Zn or Al,

(b-IX) a terpene derivative,

(b-X) an inorganic oxidant, (b-XI) a compound containing a group o Il

— ^cx

N-O- C

O which is different from component (b-l), (b-XI I) an acrylate polymer or copolymer or an acrylate derivative polymer or copolymer.

13. A composition according to claim 1 wherein component (a) is a thermoplastic natural or synthetic polymer.

14. A composition according to claim 1 wherein component (a) is a polyolefin homo- or copolymer, a starch modified polyolefin or a starch based polymer composite.

15. A composition according to claim 1 wherein component (a) is polyethylene, polypropylene, a polyethylene copolymer or a polypropylene copolymer.

16. An article made of a composition as defined in claim 1.

17. An article according to claim 16, which is an agricultural article.

18. An article according to claim 16, which is an agricultural article selected from the group consisting of mulch films, small tunnel films, row covers, banana bags, direct covers, nonwoven, twines and pots.

19. An article according to claim 16, which is a monolayer or three-layers mulch film having a thickness of 5 to 100 microns and optionally being partly buried with soil.

20. An article according to claim 16, which is a packaging material and/or which is used for consumer products.

21. An article according to claim 16, which is a packaging material for food, beverage or cosmetics.

22. An article according to claim 16, which is a hygienic or medical article.

23. An article according to claim 16, which is selected from the group consisting of films, fibers, profiles, bottles, tanks, containers, sheets, bags, styrofoam cups, plates, blister packages, boxes, package wrappings and tapes.

24. An article according to claim 16, which is shaped by injection-molding, blow-molding, compression-molding, roto-molding, slush-molding, extrusion, film casting, film blowing, calendering, thermoforming, spinning or rotational casting.

25. A degradation accelerator mixture comprising components (b-l) and component (b-ll) as defined in claim 1.

26. A method for controlling the weathering resistance and the degradation of an organic polymer, which method comprises incorporating into the organic polymer component (b-l) optionally in combination with component (b-ll) as defined in claim 1.

27. A compound of the formula