Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
  • C08K5/1575—Six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/20—Carboxylic acid amides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethylene

Definitions

• Polyethylene may for instance be processed by blown moulding, blown film or by the extrusion techniques.
• properties such as melt strength and melt elasticity are often important.
• Properties such as drawability can also be important during the processing of polyethylene, especially when producing fibres, typically as spun melt or continuous filament, or when producing blown films, typically involving extrusion of the polyethylene through a blown film extruder machine.
• US 2011/0171407 A1 discloses a method for increasing the melt strength of a polyethylene resin by reacting the polyethylene resin with an alkoxy amine derivative of the formula: (R1) (R2) N - O - R3 where R1 and R2 are each independently of one another hydrogen, C4-C42 alkyl or C4-C42 aryl or substituted hydrocarbon groups comprising O and/or N, and where R1 and R2 may form a ring structure together; and where R3 is hydrogen, a hydrocarbon or a substituted hydrocarbon group comprising O and/or N.
• melt strength is a practical measurement that can predict material performance when submitted at elongational deformations.
• US 10865298 B2 describes a composition that includes polyethylene, a multifunctional co-agent having a functionality of 3 or greater, where the multifunctional co-agent is from 100 to 2000 ppm based upon the polyethylene, and a free radical generator, where the fee radical generator is from 5 to 100 ppm based upon the polyethylene.
• This reference describes that in addition to an improved gel count, high melt strengths may be desirable for polyethylene.
• US 10844210 B2 teaches a method for increasing the melt strength and/or low shear viscosity of a polyethylene resin.
• the method comprises: a) providing a first polyethylene resin having a density ranging from 0.900 g/cm 3 to 0.970 g/cm 3 , a melt index ranging from 0.01 g/10 min to 30 g/10 min, and at least 0.20 vinyl groups per 1000 total carbons; b) providing a masterbatch composition comprising a free radical generator and a second polyethylene resin.
• the free radical generator has a half-life at 220°C, of less than 200 seconds, and a decomposition energy higher than -250 kJ/mol.
• WO 2014/043184 A1 relates to a film structure comprising an outer layer, a core and an inner layer (or sealant layer).
• the outer layer comprises a polyolefinic material having a Vicat softening temperature of 85°C or greater, most preferably 90°C or greater, and a total crystallinity in the range of 25 to 45%.
• the core is a linear low- density polyethylene having a density of 0.925 g/cm 3 or less, and a melt index of 4.0 g/10 min or less.
• the inner layer (or sealant layer) comprises linear low-density polyethylene having a density of from 0.865 to 0.926 g/cm 3 and a melt index of less than 4.0/10 minutes.
• the films are said to be further characterised by having the total amount of polyethylene having a density of 0.930 g/cm 3 or greater which makes up the film being of less than 25% by weight of the entire film.
• the description reveals that the core may comprise a single layer or, more preferably, multiple layers, with additional layers adding functionality such as barrier properties, melt strength or additional toughness depending on the intended application for the film.
• US 9278487 B1 discloses an extruded air-cooled blown film having a) a total thickness of 5 to 500 pm, b) a monolayer structure of 2 to 9 co-extruded layers, c) at least one layer containing a polymer selected from polypropylene homopolymers, polypropylene random copolymers, hetero phasic polypropylene block polymers, or any mixtures, and optionally d) a modulus according to EN ISO 527 enhanced by at least 10% versus a reference film without the nucleating agent.
• the polymer of the at least one layer has a melt flow rate, according to ASTM D-1238, of 0.1 to 10 dg/min at 230°C and 2.16 kg.
• An objective of the present invention is to provide improvements to melt strength and/or melt elasticity and/or the drawability of polyethylenes.
• Such improvements are desirable for mono and biaxial orientated polyethylene films (BOPE).
• Yo is a residue which is formed by elimination of y amino groups of a saturated or unsaturated aliphatic polyamine having 3 to 25 carbon atoms, a residue which is formed by elimination of y amino groups of a saturated or unsaturated alicyclic polyamine having 6 to 25 carbon atoms or a residue which is formed by elimination of y amino groups of an aromatic polyamine having 6 to 25 carbon atoms; any of said polyamines optionally contains further hetero atoms in its skeleton;
• Zo is a residue which is formed by elimination of z' amino groups and z" carboxyl groups of an unsaturated or saturated aliphatic amino carboxylic acid having 2 to 25 carbon atoms, a residue which is formed by elimination of z' amino groups and z" carboxyl groups of a saturated or unsaturated alicyclic amino carboxylic acid having 7 to 25 carbon atoms or a residue which is formed by elimination of z' amino groups and z" carboxyl groups of an aromatic amino carboxylic acid having 7 to 25 carbon atoms; any of said amino carboxylic acids optionally contains further hetero atoms in its skeleton; the radicals Z1 and Z2 independently of one another have the same definition given for Xi.
• Examples of a saturated or unsaturated alicyclic polycarboxylic acid having 7 to 25, preferably 8 to 16, carbon atoms and x carboxyl groups and optionally containing further hetero atoms in its skeleton are 1 ,2-cyclohexane dicarboxylic acid, 1 ,4-cyclohexanedicarboxylic acid, 1 ,4-cyclohexanediacetic acid, cyclohexanetricarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cy clo hexa netetra carb oxy lie acid, tetrahydrofurantetracarboxylic acid, 5-(succinic acid)-3-methyl-3-cylohexene-1 ,2- dicarboxylic acid, bicyclo[2,2,2]octa-7-ene-2,3,5,6-tetracarboxylic acid, 5,6,9,10- tetracar
• Examples of an aromatic polycarboxylic acid having 8 to 25, preferably 8 to 22, in particular 8 to 17, carbon atoms and x carboxyl groups and optionally containing further hetero atoms in its skeleton are p-phenylenediacetic acid, p- phenylenediethanoic acid, phthalic acid, 4-tert-butylphthalic acid, isophthalic acid, 5-tert-butylisophthalic acid, terephthalic acid, 1 ,8- naphthalic acid, 1 ,4- naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7- naphthalenedicarboxylic acid, diphenic acid, 3,3'-biphenyldicarboxylic acid, 4,4'- biphenyldicarboxylic acid, 4,4'-binaphthyldicarboxylic acid, bis(3- carboxyphenyl)methane, bis(4-carboxyphenyl
• linear or branched alkyl having up to 20 carbon atoms and being optionally substituted by one or more hydroxy, amino and/or nitro groups are ethyl, n-propyl, 1 -methylethyl, n-butyl, 2-methylpropyl, 1 -methyl propyl, tert-butyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 1 ,1 -dimethylpropyl, 1- ethylpropyl, tert-butyl methyl, hexyl, 1 -methylpentyl, heptyl, isoheptyl, 1- ethylhexyl, 2-ethylpentyl, 1-propylbutyl, octyl, nonyl, isononyl, neononyl, 2,4,4- trimethylpentyl, undecyl, tridecyl, pentadecyl
• Branched C 3 -Cioalkyl is particularly preferred.
• One of the preferred meanings of the radicals Xi, Yi, Zi and Z2 is branched C3-C10 alkyl with a quaternary C atom in position 1 , in particular -C(CHs)2-H or -C(CH 3 )2-(Ci-C 7 alkyl).
• C 2 -C 2 oalkyl interrupted by oxygen or sulfur are t-butoxym ethyl, t- butoxyethyl, t-butoxypropyl, t-butoxybutyl, (H 3 C) 3 C-S-CH 2 -, (H 3 C) 3 C-S-C 2 H 4 -, (H 3 C)3C-S-C 3 H5- and (H 3 C) 3 C-S-C 4 H 8 -.
• Ci-Csalkoxy examples are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy and octyloxy. Methoxy is particularly preferred.
• Ci-Csalkylthio examples include methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio and octylthio.
• Ci-Csalkylsulfoxy examples are methylsulfoxy, ethylsulfoxy, propylsulfoxy, butylsulfoxy, pentylsulfoxy, hexylsulfoxy, heptylsulfoxy and octylsulfoxy.
• Ci-C 2 oalkenyl unsubstituted or substituted by one or more hydroxy, amino and/or nitro groups are 9-decenyl, 8-heptadecenyl, 11-hydroxy-8- heptadecenyl and 11-amino-8-heptadecenyl.
• Ci- C 2 oalkyl unsubstituted or substituted by one or more Ci- C 2 oalkyl, e.g. 1 , 2, 3 or 4 Ci-C 4 alkyl, are cyclopropyl, 3-methylcyclopropyl, 2,2,3,3-tetramethylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1- methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4- tert-butylcyclohexyl and cycloheptyl.
• Ci-C 2 oalkyl e.g. 1 , 2 or 3 Ci-C 4 alkyl
• Ci-C 2 oalkyl e.g. 1 , 2 or 3 Ci-C 4 alkyl
• Ci-C 2 oalkyl examples of a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Ci-C 2 oalkyl, e.g. 1 , 2 or 3 Ci-C 4 alkyl, are examples of a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Ci-C 2 oalkyl, e.g. 1 , 2 or 3 Ci-C 4 alkyl, are examples of a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Ci-C 2 oalkyl, e.g. 1 , 2 or 3 Ci-C 4 alkyl, are examples of a bicyclic or tricyclic hydrocarbon radical with 5 to 20 carbon atoms unsubstituted or substituted by one or more Ci-C 2 oalkyl, e.g.
• Ci- C 20 alkyl e.g. 1 , 2 or 3 Ci-C4alkyl
• Ci- C 20 alkyl e.g. 1 , 2 or 3 Ci-C4alkyl
• biphenylenyl, fluorenyl or anthryl is 2-biphenylenyl, 9-fluorenyl, 1- fluorenyl or 9-anthryl, respectively.
• tri(Ci-Ci O alkyl)silyl is (H 3 C)3Si-.
• Examples of an aromatic polyamine having 6 to 25, preferably 6 to 17, in particular s to 13, carbon atoms and y amino groups and optionally containing further hetero atoms in its skeleton are o-phenylenediamine, m- phenylenediamine, p-phenylenediamine, 2,3-diaminotoluene, 2,4- diaminotoluene, 2,6-diaminotoluene, 3,4-diaminotoluene, 4,6-dimethyl-m- phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 4,5-dimethyl-o- phenylenediamine, 2,4-diaminomesitylene, 2,3-diaminopyridine, 2,6- diaminopyridine, 3,4-diaminopyridine, 1 ,5-diaminonaphthalene, 1 ,8- diaminonaphthalene, 2,3-
• the additive is a bisamide or a trisamide of formula (IB) wherein when the additive is a bisamide Yo is represented by formula (III) or formula (II) and when the additive is a trisamide Yo is represented by formula (V). More preferably, the additive is a trisamide of formula (IB) wherein Yo is represented by formula (V). It is particularly preferred that the additive is an aromatic trisamide of formula (VII), in which R1 , R2 and R3 each independently selected from C1-C5 linear or branched alkyl or substituted or unsubstituted C3-C6 cycloalkyl, preferably R1 , R2 and R3 all being tertiary butyl. In this case, R1 , R2 and R3 represent each Y1 of formula (IB).
• R1 is a substituted cyclohexyl group.
• R1 has the structure shown in formula (VII A):
• W may be selected from C1-C10 linear or branched substituted or unsubstituted alkyl and may be in any substitution position of the cyclohexyl group, preferably in the para-position.
• R2 and R3 would have the same definitions given for the structure of formula (VII).
• W is located in the para- position and is in the cis-position relative to the bond of the carbonyl carbon attached to the cyclohexanediyl ring.
• W is located in the para-position and is in the trans-position relative to the bond of the carbonyl carbon attached to the cyclohexanediyl ring.
• R2 has independently of R1 the same definition as ascribed to R1 as represented by formula (VII A).
• both R2 and R3 independently of each other and R1 have the same definition as ascribed to R1 as represented by formula (VII A).
• a further specific suitable compound according to formula (VII B) is cis-4-tert- butylcyclohexylcarbonylamino-3,5-bis[trans-4-tert-butylcyclohexylcarbonylamino] benzene, illustrated by formula (XVII):
• a still further specific suitable compound according to formula (VII B) is 1 , 3, 5- tris[trans-4-tert-butylcyclohexylcarbonylamino] benzene, illustrated by formula
• Additional specific suitable compounds according to formula (VII B) are 1 ,3,5-tris[cis- 4-iso-propycyclohexylcarbonylamino]benzene, trans-4-iso- propylylcyclohexylcarbonylamino-3,5-bis [cis-4-iso-propylcyclohexylcarbonylamino] benzene, trans-4-iso-propylcyclohexylcarbonylamino-3,5-bis [cis-4-iso-propyl cyclohexylcarbonylamino] benzene and 1 , 3, 5-tris[trans-4-iso-propylcyclohexyl carbonylamino] benzene.
• the additive may desirably be a sorbitol acetal.
• the sorbitol acetal is a compound based on formula (VIII): wherein p is zero or 1 ; m and n independently of one another are an integer from 0 to 3; each radical R independently one another are Ci-Cs alkyl, Ci-Cs alkoxy, hydroxy, halogen, pseudo-halogen, Ci-Cs alkylthio, Ci-Cs alkylsulfoxy or 2 radicals R form together with two adjacent carbon atoms of the unsaturated parent ring a 5 to 7 membered carbocyclic or heterocyclic ring and R1 is selected from hydrogen or Ci- C3 alkyl.
• halogen or pseudo-halogen examples include -F, -Cl, -Br, -I, -CN, -CNO, - OCN, -SCN and -CNS.
• a compound according to formula (VIII) includes two radicals R forming together with two adjacent carbon atoms of the unsaturated parent ring a 5 to 7-membered carbocyclic or heterocyclic ring is represented by formula (XX):
• the additive may be added to the polyethylene melt in any suitable amount.
• the polyethylene comprises the additive in an amount of from 0.001 to 1 .0%, suitably from 0.002 to 0.75% weight of additive to weight of polyethylene, preferably from 0.005 to 0.5%.
• One particularly suitable range may for instance be from 0.005 to 0.05%.
• Another particularly suitable range may be for instance from 0.05 to 0.5%.
• Bisamides, trisamides and tetraamides may suitably be added in any of these ranges.
• bisamides, trisamides and tetraamides may be added in the range from 0.005 to 0.1 % more preferably from 0.005 to 0.02%.
• Sorbitol acetals may suitably be added in any of these ranges.
• sorbitol acetals may be added in the range from 0.1 to 0.6%, more preferably from 0.15 to 0.5%.
• the polyethylene produced according to the present invention may be produced as a polyethylene film, a polyethylene fiber or other articles of polyethylene.
• the polyethylene produced according to the present invention is a polyethylene film.
• the polyethylene melt may optionally contain one or more co-additives commonly used in the plastics’ industry.
• co-additives may be at least one selected from the group consisting of UV absorbers and light stabilisers; antioxidants; vis-breaking agents; metal deactivators; phosphites and phosphonites; nitrones; thiosynergists; peroxide scavengers; basic co-stabilisers; nucleating agents; fillers and reinforcing agents; other additives; and benzofuranones and indolinones.
• co- additives include slip additives, acid scavengers, for instance as described in Chapter 4 of the Plastic Additives Handbook; lubricants, for instance as described in Chapter 5 of the Plastic Additives Handbook polymer processing aids, for instance as described in Chapter 6 of the Plastic Additives Handbook; anti blocking additives, for instance as given in Chapter ? of the Plastic Additives Handbook; and antifogging additives, for instance as given in Chapter 9 of the Plastic Additives Handbook.
• slip additives for instance as described in Chapter 4 of the Plastic Additives Handbook
• lubricants for instance as described in Chapter 5 of the Plastic Additives Handbook
• polymer processing aids for instance as described in Chapter 6 of the Plastic Additives Handbook
• anti blocking additives for instance as given in Chapter ? of the Plastic Additives Handbook
• antifogging additives for instance as given in Chapter 9 of the Plastic Additives Handbook.
• 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-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4- methylphenol, 2-(a-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-T
• 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.
• 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-octadecyloxyphenol, 2,6-di-tert- butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4- hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4- hydroxyphenyl) adipate.
• 2,6-di-tert- butyl-4-methoxy phenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert- amylhydroquinone, 2,6-diphen
• Tocopherols for example a-tocopherol, -tocopherol, y-tocopherol, o- tocopherol and mixtures thereof (vitamin E).
• 1 .5. Hydroxylated thiodiphenyl ethers for example 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.
• 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-(a-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-(a- methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(a,a-dimethylbenzyl)-4-
• 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-3,5-di-tert-butyl-4- hydroxybenzylmercaptoacetate.
• Hydroxybenzylated malonates for example dioctadecyl-2, 2-bis(3, 5- di-tert-butyl-2-hydroxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5- methylbenzyl)malonate, di dodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4- hydroxybenzyl)malonate, bis[4-( 1 , 1 ,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di- tert-butyl-4-hydroxybenzyl)malonate.
• 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-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4- hydroxybenzyl)phenol.
• 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)-
• Benzylphosphonates for example dimethyl-2,5-di-tert-butyl-4- hydroxybenzylphosphonate, diethyl-3, 5-di-tert-butyl-4- hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3- methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3, 5-di-tert- butyl-4-hydroxybenzylphosphonic acid.
• esters of 13-(3,5-di-tert-butyl-4-hydroxyphenyl)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, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3- thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol propane, 4- hydroxymethyl-1-phospha-2,6,7-trio
• esters of 13-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or poly hydric 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, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis- (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7- triox
• esters of 13-(3,5-dicyclohexyl-4-hydroxyphenyl)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, tri ethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl- 1-phospha-2,6,7-trioxabicyclo[2.2.2]oct
• esters of 3,5-di-tert-butyl-4-hydroxyphenyl 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 droxym ethyl- 1- phospha-2,6,7-trioxabicyclo
• Aminic antioxidants for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p- phenylenediamine, N,N'-bis(1-ethyl-3- methylpentyl)-p-phenylenediamine, N,N'- bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p phenylenediamine, N- isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl)-N'-
• 2-(2'-Hydroxyphenyl)benzotriazoles for example 2-(2'-hydroxy-5'- methylphenyl)-benzo triazole, 2-(3',5'-di-tert-butyl-2'- hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2- (2'-hydroxy-5'-(1 , 1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di tert- butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'- methylphenyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'- hydroxyphenyl)benzotriazole, 2-(2' hydroxy-4'
• R 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-hydroxy-3'-(a,a- dimethylbenzyl)-5'-(1 , 1 ,3,3-tetramethylbutyl)-phenyl] benzotriazole; 2-[2'- hydroxy-3'-(1 , 1 ,3,3-tetramethylbutyl)-5'-(a,a-dimethylbenzyl)-phenyl]ben zotriazole.
• Esters of substituted and unsubstituted benzoic acids for example 4- tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert- butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4- hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di- tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
• 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 ketoxi mes, e.g. of 2-hydroxy-4- methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5- hydroxypyrazole, with or with out additional ligands.
• additional ligands such as n butylamine, triethanolamine or N- cyclohexyldiethanol
• Sterically hindered amines for example 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 octyla
• 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.
• 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(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
• N,N'-diphenyloxamide
• 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, diisodecylpentaerythritol 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 diphos
• Tris(2,4-di-tert-butylphenyl) phosphite (lrgafos®168, BASF SE), tris(nonylphenyl) phosphite,
• 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 or derived from vegetable source.
• 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-alpha-heptadecylnitrone, N- ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta decylnitrone, N- octadecyl-alpha-hexadecylnitrone, nitrone derived from
• Thiosynergists for example dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis[3- (dodecylthio)propionate] or distearyl disulfide.
• Peroxide scavengers for example esters of -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(p -dodecylmercapto)propionate.
• esters of -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(p -dodecyl
• 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.
• 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 ric
• 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).
• 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 copoly
• Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibers, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, car bon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
• additives for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
• Other additives may also include anti-block additives, as referred to above, which are used in films to reduce the negative adhesion of two polyethylene surfaces to one another which would otherwise result in difficulties separating the films.
• Further additives include slip additives, as referred to above, which are used to help the film surfaces slide over each other.
• Antifogging agents as referred to above, may also be added.
• Benzofuranones and indolinones for example those disclosed in U.S. 4,325,863; U.S.
• Vis-breaking agents or generally radical initiators typically, this includes organic or inorganic peroxides, which are widely used in industry, bis azo compounds,
• Suitable peroxides as vis-breaking agents include 2,5-dimethyl-2,5-di(t- butylperoxy)hexane, 2,5- dimethyl-2,5-di(t-butylperoxy)hexyne-3, 3, 6, 6,9,9- pentamethyl-3-(ethyl acetate)-1 ,2,4,5- tetraoxy cyclononane, t-butyl hydroperoxide, hydrogen peroxide, dicumyl peroxide, t-butyl peroxy isopropyl carbonate, di-t-butyl peroxide, p-chlorobenzoyl peroxide, dibenzoyldiperoxide, t-butyl cumyl peroxide; t-butyl hydroxyethyl peroxide, di-t- amyl peroxide and 2,5- dimethylhexene-2,5-diperisononanoate, acetylcyclohexanesulphon
• Such azo compounds are for example 2,2'-azobisisobutyronitrile, 2,2'-azobis(2- methylbutyronitrile ), 2,2'-azobis(2,4-dimethylvaleronitrile ), 2,2'-azobis( 4-methoxy- 2,4-dimethylvaleronitrile ), 1 , 1 '-azobis(1 -cyclohexanecarbonitrile ), 2,2'- azobis(isobutyramide)dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, dimethyl 2,2'-azobisisobutyrate, 2-( carbamoylazo )isobutyronitrile, 2,2'-azobis(2,4,4- trimethylpentane ), 2,2'-azobis(2-methylpropane), 2,2'-azobis(N,N'- dimethyleneisobutyramidine) as free base or hydrochloride, 2,2'azobis(2- amidinoprop
• the co-additive is for example present in the polymer melt in an amount of 0.001 to 10 % by weight, preferably 0.001 to 5 % by weight, relative to the weight of the polyethylene.
• Conventional fillers or reinforcing agents may be present in the polymer melt in amounts of 0.1 to 10 % by weight, preferably 1 to 5 % by weight, in certain cases in amounts up to 70 % by weight, relative to the weight of the polyethylene.
• 120micron films were produced on a Colling Cast film line CR 136 / 230 at 230°C.

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