Laser printable polymeric compositions

Abstract

A polymeric composition includes an ethylene polymer, 0.05 wt% to 0.25 wt% carbon black based on a total weight of the polymeric composition and a polymeric ultraviolet light stabilizer including a hindered amine moiety and having a weight average molecular weight from 5,000 g / mol to 20,000 g / mol as measured according to Gel Permeation Chromatography.

Description

BACKGROUNDField of the disclosure

[0001] The present disclosure relates to compositions, and more specifically, topolymeric compositions that are laser printable.Introduction

[0002] Laser beam printing is a method used in the marking of polymericcompositions. Laser beam printing is useful because no printing ink or physicalcontact between the polymeric composition and the printer are required. Further,the process of laser beam printing is fast and simple and can provide a marking ofgood durability.

[0003] Not every polymeric composition can be laser printed. For example,polymeric compositions often require specific additives and compositions in orderto be rendered laser printable. The requirements to render a polymericcomposition laser printable may be in conflict with the design of the polymericcomposition based on its end use. For example, conventional wire and cablejacketing may include carbon black in concentrations from about 2 weight percentto 3 weight percent to ensure 50% retention of elongation at break after 2000hours of accelerated ultraviolet exposure. Unfortunately, conventional carbonblack concentrations of about 2 weight percent to 3 weight percent lead toinsufficient contrast (i.e., 25% contrast or less) when laser printing.

[0004] Others have attempted to solve the afore mentioned issue by replacingcarbon black with ultraviolet ("UV") light stabilizers. For example, EuropeanPatent Office Patent Publication Number EP0710570A1 ("'570 publication")discloses a grouping of UV light stabilizers that allow for low carbon blackconcentrations and provide a laser printable jacketing. The disclosed UV lightstabilizers of the '570 publication are (a) a dimethyl succinate polymer with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol, (b) 2-(2'-hydroxy-5'-tbutylphenyl)-3-chlorobenzotriazole, (c) 2-hydroxy-4-m-octoxybenzophenone, (d)N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine polymer with2,4,6-trichloro-1,3,5-triazine and 2,4,4-trimethyl-1,2-pentanamine, (e) 2-(3',5'-ditert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, (f) bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and (g) 2H-1-benzopyran-2-one, 7-(2Hnaphtho[1,2D]triazol-2-yl)-3-phenyl. The disclosed UV light stabilizers of the'770 publication are either small molecules or oligomeric in nature. For example,UV light stabilizers (b), (c), (e), (f) and (g) are all small molecules whereas (a) hasa number average molecular weight (Mn) from 3100 to 4000 and (d) has an Mn of2000 to 3100 rendering (a) and (d) oligomeric. As demonstrated in Table 5 of the'570 publication, example 17A utilizing oligomeric UV light stabilizer (a) is ableto produce a polymeric composition that can withstand accelerated UV lightexposure with less than 2 weight percent but greater than 0.3 weight percentcarbon black. However, Table 3 of the '570 publication demonstrates oligomericUV light stabilizer (a) fails to reach a grey contrast above 25% at carbon blacklevels of 0.3 weight percent or greater. These results suggest that the use ofpolymeric ultraviolet light stabilizers comprising a hindered amine moieties require acompromise between compositions that withstand accelerated UV light exposureand laser printable compositions.

[0005] Another attempt in the art to solve the issues related to laser printing wireand cable jacketing is provided by World Intellectual Property OrganizationPublication Number WO2019068815A1 ("'815 publication") and utilizes carbonblack and a synergistic blend of oligomeric hindered amine UV light stabilizers.The '815 publication discloses the use of a synergistic mixture of UV lightstabilizers (a) and (d) of the '570 publication in a polymeric composition, butrequires at least a 0.25 weight percent carbon black concentration to retain themechanical properties of the polymeric composition after accelerated UVexposure.

[0006] In view of the combined art's inability to achieve a polymeric compositionutilizing less than 0.25 weight percent carbon black through the addition of anoligomeric hindered amine light stabilizer, it would be surprising to discover apolymeric composition that comprises 0.05 wt% to 0.25 wt% of carbon black and a25 polymeric ultraviolet light stabilizer having a weight average molecular weight from5,000 g / mol to 20,000 g / mol as measured according to Gel PermeationChromatography that is laser printable (i.e., grey contrast of greater than 25%) andretains 50% or more of its elongation at break after 2000 hours of acceleratedultraviolet exposure.SUMMARY OF THE DISCLOSURE

[0007] The inventors of the present application have surprisingly discovered that theuse of a polymeric ultraviolet light stabilizer comprising a hindered amine moiety andhaving a weight average molecular weight from 5,000 g / mol to 20,000 g / mol asmeasured according to Gel Permeation Chromatography enables the formation of apolymeric composition having 0.05 weight percent to 0.25 weight percent carbonblack that is laser printable (i.e., grey contrast of greater than 25%) and retains 50% ormore of its elongation at break after 2000 hours of accelerated UV light exposure.Without being bound by theory, it is believed that the higher molecular weight of thepolymeric UV light stabilizer, as opposed to the oligomeric UV light stabilizers of theprior art, resists migration and segregation during manufacturing and use of thepolymeric composition. The reduced migration of the polymeric UV light stabilizerprovides enhanced preservation to the stabilizer during extended exposure to UVlight. As a result of the enhanced preservation and maintained dispersion of thestabilizer, the polymeric composition is able to retain 50% or more of its elongation atbreak after 2000 hours of accelerated UV light exposure. The successful use of apolymeric UV light stabilizer is surprising given that it would be expected that equalweight percent of oligomeric stabilizer would be successful, but are not asdemonstrated by the prior art. As the UV light stabilizer remains dispersed and allowsthe polymeric composition to retain its elongation at break, a lower loading of carbonblack can be used that renders the polymeric composition laser printable.

[0008] The polymeric composition is particularly useful as a jacketing for wires andcables.

[0009] According to a first feature of the present disclosure, a polymeric compositioncomprises an ethylene polymer, 0.05 wt% to 0.25 wt% carbon black based on a totalweight of the polymeric composition, and a polymeric ultraviolet light stabilizercomprising a hindered amine moiety and having a weight average molecular weightfrom 5,000 g / mol to 20,000 g / mol as measured according to Gel PermeationChromatography.

[0010] According to a second feature of the present disclosure the polymericcomposition comprises 95 wt% or greater of the ethylene polymer based on a totalweight of the polymeric composition.

[0011] According to a third feature of the present disclosure the ethylene polymer hasa density of from 0.919 g / cc to 0.950 g / cc as measured by ASTM D792.

[0012] According to a fourth feature of the present disclosure the polymericcomposition further comprises an oligomer ultraviolet light stabilizer having a weightaverage molecular weight of from 1,000 g / mol to 5,000 g / mol as measured accordingto Gel Permeation Chromatography.

[0013] According to a fifth feature of the present disclosure the polymericcomposition comprises from 0.25 wt% to 1.0 wt% of the oligomer ultraviolet lightstabilizer based on a total weight of the polymeric composition.

[0014] According to a sixth feature of the present disclosure the oligomer ultravioletlight stabilizer has a chemical abstract services registration number of 136504-96-6 or71878-19-8.

[0015] According to a seventh feature of the present disclosure the polymericcomposition comprises from 0.10 wt% to 0.25 wt% carbon black based on a totalweight of the polymeric composition.

[0016] According to an eighth feature of the present disclosure the polymericcomposition comprises from 0.25 wt% to 2 wt% of the polymeric ultraviolet lightstabilizer based on a total weight of the polymeric composition.

[0017] According to a ninth feature of the present disclosure the polymeric ultravioletlight stabilizer has a weight average molecular weight from 8,000 g / mol to 12,000g / mol as measured according to Gel Permeation Chromatography, further wherein thepolymeric ultraviolet light stabilizer has a chemical abstract services registrationnumber of 136504-96-6.

[0018] According to a tenth feature of the present disclosure a coated conductorcomprises a conductor and the polymeric composition disposed at least partiallyaround the conductor.DETAILED DESCRIPTION

[0019] As used herein, the term "and / or," when used in a list of two or moreitems, means that any one of the listed items can be employed by itself, or anycombination of two or more of the listed items can be employed. For example, if acomposition is described as containing components A, B, and / or C, thecomposition can contain A alone; B alone; C alone; A and B in combination; Aand C in combination; B and C in combination; or A, B, and C in combination.

[0020] All ranges include endpoints unless otherwise stated.

[0021] Test methods refer to the most recent test method as of the priority date ofthis document unless a date is indicated with the test method number as ahyphenated two-digit number. References to test methods contain both a referenceto the testing society and the test method number. Test method organizations arereferenced by one of the following abbreviations: ASTM refers to ASTMInternational (formerly known as American Society for Testing and Materials);EN refers to European Norm; DIN refers to Deutsches Institut fur Normung; andISO refers to International Organization for Standards. When used herein,Chemical Abstract Services registration numbers refer to the most recent chemicalor chemical composition designated for that registration number as of the prioritydate of this document.

[0022] As used herein, the term weight percent ("wt%") designates the percentageby weight a component is of a total weight of the polymeric composition unlessotherwise indicated. The term mole percent ("mol%") designates the percentageby moles a component is of a total moles of the item in which the component ispresent.

[0023] Unless otherwise provided herein, density is measured in accordance withASTM D792, Method B. The result is recorded in grams (g) per cubic centimeter(g / cc).

[0024] Unless otherwise provided herein, a melt index (MI) is measured inaccordance with ASTM D1238, Condition 190°C / 2.16 kilogram (kg) weight and isreported in grams eluted per 10 minutes (g / 10 min).

[0025] "Polymer" means a polymeric compound prepared by polymerizingmonomers, whether of the same or a different type. The generic term polymerthus embraces the terms homopolymer, interpolymer and copolymer.Polymeric Compositions

[0026] The present disclosure provides a polymeric composition. The polymericcomposition comprises an ethylene polymer, carbon black and a polymeric ultravioletlight stabilizer ("polymeric stabilizer"). The polymeric composition may alsocomprise an oligomer ultraviolet light stabilizer ("oligomeric stabilizer"). As will beexplained in greater detail below, the polymeric composition may be utilized to forma jacket of a coated conductor.Ethylene polymer

[0027] The polymeric composition comprises the ethylene polymer. The ethylenepolymer may comprise 50 mol% or greater, 60 mol% or greater, 70 mol% orgreater, 80 mol% or greater, 85 mol% or greater, 90 mol% or greater, or 91 mol%or greater, or 92 mol% or greater, or 93 mol% or greater, or 94 mol% or greater,or 95 mol% or greater, or 96 mol% or greater, or 97 mol% or greater, or 97.5mol% or greater, or 98 mol% or greater, or 99 mol% or greater, while at the sametime, 100 mol% or less, 99.5 mol% or less, or 99 mol% or less, or 98 mol% orless, or 97 mol% or less, or 96 mol% or less, or 95 mol% or less, or 94 mol% orless, or 93 mol% or less, or 92 mol% or less, or 91 mol% or less, or 90 mol% orless, or85 mol% or less, or 80 mol% or less, or 70 mol% or less, or 60 mol% or less ofethylene as measured using Nuclear Magnetic Resonance (NMR) or FourierTransform Infrared (FTIR) Spectroscopy. Other units of the ethylene polymermay include C3 to C4, or C6, or C8, or C10, or C12, or C16, or C18, or C20 α-olefins,such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Otherunits of the ethylene polymer may be derived from one or more polymerizablemonomers including, but not limited to, polar monomers such as unsaturatedesters. The unsaturated esters may be alkyl acrylates, alkyl methacrylates, or vinylcarboxylates. The alkyl groups can have from 1 to 8 carbon atoms, or from 1 to 4carbon atoms. The carboxylate groups can have from 2 to 8 carbon atoms, or from2 to 5 carbon atoms. Examples of acrylates and methacrylates include, but are notlimited to, ethyl acrylate, methyl acrylate, methyl methacrylate, t-butyl acrylate, nbutyl acrylate, n-butyl methacrylate, and 2 ethylhexyl acrylate. Examples of vinylcarboxylates include, but are not limited to, vinyl acetate, vinyl propionate, andvinyl butanoate. The ethylene polymer may have a polar monomer content of 40wt% or less, or 35 wt% or less, or 30 wt% or less, or 25 wt% or less, or 20 wt% or40 less,15 wt%, or 10 wt%, or 5 wt% or less, or 3 wt% or less, or 1 wt% or less, or 0wt% based on the total weight of the ethylene polymer as measured using NuclearMagnetic Resonance (NMR) or Fourier-Transform Infrared (FTIR) Spectroscopy.

[0028] The density of the ethylene polymer may be 0.900 g / cc or greater, or 0.904g / cc or greater, or 0.910 g / cc or greater, or 0.915 g / cc or greater, or 0.919 g / cc orgreater, or 0.920 g / cc or greater, or 0.921 g / cc or greater, or 0.922 g / cc or greater,or 0.925 g / cc or greater, or 0.926 g / cc or greater, or 0.930 g / cc or greater, or 0.935g / cc or greater, 0.940 g / cc or greater, 0.945 g / cc or greater, while at the same time,0.950 g / cc or less, or 0.940 g / cc or less, or 0.935 g / cc or less, or 0.930 g / cc or less,or 0.925 g / cc or less, or 0.920 g / cc or less, or 0.919 g / cc or less, or 0.915 g / cc orless, or 0.910 g / cc or less, or 0.905 g / cc or less as measured according to ASTMD792.

[0029] The melt index of the ethylene polymer may be 0.1 g / 10 min or greater, or 0.3g / 10 min or greater, or 0.5 g / 10 min or greater, or 1.0 g / 10 min or greater, or 1.5 g / 10min or greater, or 2.0 g / 10 min or greater, or 2.5 g / 10 min or greater, or 3.0 g / 10 minor greater, or 3.5 g / 10 min or greater, or 4.0 g / 10 min or greater, or 4.5 g / 10 min orgreater, or 10.0 g / 10 min or greater, or 18 g / 10 min or greater, while at the same time,30.0 g / 10 min or less, or 25.0 g / 10 min or less, or 20.0 g / 10 min or less, or 18.0 g / 10min or less, or 15.0 g / 10 min or less, or 10.0 g / 10 min or less, or 5.0 g / 10 min or less,or 4.5 g / 10 min or less, or 4.0 g / 10 min or less, or 3.5 g / 10 min or less, or 3.0 g / 10min or less, or 2.5 g / 10 min or less, or 2.0 g / 10 min or less, or 1.5 g / 10 min or less, or1.0 g / 10 min or less, or 0.5 g / 10 min or less as measured according to ASTM D1238.

[0030] The polymeric composition comprises from 80 wt% to 99 wt% of theethylene polymer. For example, the polymeric composition may comprise 80 wt% orgreater, or 82 wt% or greater, or 84 wt% or greater, or 86 wt% or greater, or 88 wt%or greater, or 90 wt% or greater, or 92 wt% or greater, or 94 wt% or greater, or 95wt% or greater, or 96 wt% or greater, or 98 wt% or greater, while at the same time, 99wt% or less, or 98 wt% or less, or 96 wt% or less, or 95 wt% or less, or 94 wt% orless, or 92 wt% or less, or 90 wt% or less, or 88 wt% or less, or 86 wt% or less, or 84wt% or less, or 82 wt% or less of the ethylene polymer based on the total weight ofthe polymeric composition.Carbon Black

[0031] The polymeric composition comprises carbon black. Carbon black has aChemical Abstract Services ("CAS") registration number of 1333-86-4. Thepolymeric composition may comprise the carbon black in an amount from 0.05wt% to 0.25 wt% based on a total weight of the polymeric composition. Forexample, the polymeric composition may comprise 0.05 wt% or greater, or 0.06wt% or greater, or 0.07 wt% or greater, or 0.08 wt% or greater, or 0.09 wt% orgreater, or 0.10 wt% or greater, or 0.11 wt% or greater, or 0.12 wt% or greater, or0.13 wt% or greater, or 0.14 wt% or greater, or 0.15 wt% or greater, or 0.16 wt%or greater, or 0.17 wt% or greater, or 0.18 wt% or greater, or 0.19 wt% or greater,or 0.20 wt% or greater, or 0.21 wt% or greater, or 0.22 wt% or greater, or 0.23wt% or greater, or 0.24 wt% or greater, while at the same time, 0.25 wt% or less,or 0.24 wt% or less, or 0.23 wt% or less, or 0.22 wt% or less, or 0.21 wt% or less,or 0.20 wt% or less, or 0.19 wt% or less, or 0.18 wt% or less, or 0.17 wt% or less,or 0.16 wt% or less, or 0.15 wt% or less, or 0.14 wt% or less, or 0.13 wt% or less,or 0.12 wt% or less, or 0.11 wt% or less, or 0.10 wt% or less, or 0.09 wt% or less,or 0.08 wt% or less, or 0.07 wt% or less, or 0.06 wt% or less of the carbon blackbased on a total weight of the polymeric composition.

[0032] The carbon black may have an average particle size of between about 10nm to about 300 nm, or from 10 nm to 100 nm, or from 15 nm to 50 nm asmeasured using laser diffraction spectroscopy. The carbon black may be added tothe polymeric composition as a neat, or pure component, or may be added as partof a masterbatch combined with one or more other components (e.g., resins,antioxidants and / or processing aids).Polymeric ultraviolet Light Stabilizer

[0033] The polymeric composition comprises the polymeric ultraviolet lightstabilizer. The polymeric stabilizer comprises one or more hindered amine moieties.As used herein, a hindered amine moiety is an amine moiety present on an aromaticring such that the lone pair of electrons of the nitrogen atom is conjugated into thearomatic ring. An example of a polymeric stabilizer comprising a hindered aminemoiety has a Chemical Abstract Services ("CAS") registration number of 136504-96-6 and is described as 1,3-propanediamine, N1,N1'-1,2-ethanediylbis-, polymer with2,4,6-trichloro-1,3,5-triazine, reaction products with N-butyl-2,2,6,6-tetramethyl-4-piperidinamine. A commercial example of the polymeric stabilizer is sold under thetradename UVASORBTM HA10 from 3V Sigma USA, Georgetown, South Carolina,USA. The polymeric stabilizer has a weight average molecular weight of from 5,000grams per mol ("g / mol") to 20,000 g / mol as measured according to Gel PermeationChromatography. For example, the polymeric stabilizer may have a weight averagemolecular weight of 5,000 g / mol or greater, or 6,000 g / mol or greater, or 7,000 g / molor greater, or 8,000 g / mol or greater, or 9,000 g / mol or greater, or 10,000 g / mol orgreater, or 11,000 g / mol or greater, or 12,000 g / mol or greater, or 13,000 g / mol orgreater, or 14,000 g / mol or greater, or 15,000 g / mol or greater, or 16,000 g / mol orgreater, or 17,000 g / mol or greater, or 18,000 g / mol or greater, or 19,000 g / mol orgreater, while at the same time, 20,000 g / mol or less, or 19,000 g / mol or less, or18,000 g / mol or less, or 17,000 g / mol or less, or 16,000 g / mol or less, or 15,000g / mol or less, or 14,000 g / mol or less, or 13,000 g / mol or less, or 12,000 g / mol orless, or 11,000 g / mol or less, or 10,000 g / mol or less, or 9,000 g / mol or less, or 8,000g / mol or less, or 7,000 g / mol or less, or 6,000 g / mol or less as measured according toGel Permeation Chromatography.

[0034] The polymeric composition may comprise the polymeric stabilizer in anamount from 0.25 wt% to 2.00 wt% based on a total weight of the polymericcomposition. For example, the polymeric composition may comprise 0.25 wt% orgreater, or 0.50 wt% or greater, or 0.wt% or greater, or 1.00 wt% or greater, or 1.25 wt% or greater, or 1.50 wt% orgreater, or 1.75 wt% or greater, while at the same time, 2.00 wt% or less, or 1.75wt% or less, or 1.50 wt% or less, or 1.25 wt% or less, or 1.00 wt% or less, or 0.75wt% or less, or 0.50 wt% or less of the polymeric stabilizer based on the totalweight of the polymeric composition.Oligomeric ultraviolet Light Stabilizer

[0035] The polymeric composition may comprise the oligomeric ultraviolet lightstabilizer. The oligomeric stabilizer may comprise one or more hindered aminemoieties. An example of the oligomeric stabilizer has a CAS registration numberof 136504-96-6 and is described as 1,3-propanediamine, N1,N1'-1,2-ethanediylbis-, polymer with 2,4,6-trichloro-1,3,5-triazine, reaction products withN-butyl-2,2,6,6-tetramethyl-4-piperidinamine. Such an oligomeric stabilizer issold under the tradename UVASORBTM HA88 from 3V Sigma USA,Georgetown, South Carolina, USA. Another example of the oligomeric stabilizerhas a CAS registration number 71878-19-8 and is described as poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6 hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]].Such an oligomeric stabilizer is sold under the tradename CHIMASSORBTM 944LD from BASF, Ludwigshafen, Germany.

[0036] The oligomeric stabilizer has a weight average molecular weight of from1,000 g / mol to 5,000 g / mol as measured according to Gel PermeationChromatography. For example, the polymeric stabilizer may have a weight averagemolecular weight of 1,000 g / mol or greater, or 1,500 g / mol or greater, or 2,000 g / molor greater, or 2,500 g / mol or greater, or 3,000 g / mol or greater, or 3,500 g / mol orgreater, or 4,000 g / mol or greater, or 4,500 g / mol or greater, while at the same time,5,000 g / mol or less, or 4,500 g / mol or less, or 4,000 g / mol or less, or 3,500 g / mol orless, or 3,000 g / mol or less, or 2,500 g / mol or less, or 2,000 g / mol or less, or 1,500g / mol or less as measured according to Gel Permeation Chromatography.

[0037] The polymeric composition may comprise the oligomeric stabilizer in anamount from 0.25 wt% to 2.00 wt% based on a total weight of the polymericcomposition. For example, the polymeric composition may comprise 0.25 wt% orgreater, or 0.50 wt% or greater, or 0.75 wt% or greater, or 1.00 wt% or greater, or40 1.25 wt% or greater, or 1.50 wt% or greater, or 1.75 wt% or greater, while at thesame time, 2.00 wt% or less, or 1.75 wt% or less, or 1.50 wt% or less, or 1.25wt% or less, or 1.00 wt% or less, or 0.75 wt% or less, or 0.50 wt% or less of theoligomeric stabilizer based on the total weight of the polymeric composition.Additives

[0038] The polymeric composition may include one or more additives. Nonlimitingexamples of suitable additives include antioxidants, colorants, corrosion inhibitors,lubricants, ultraviolet (UV) absorbers or stabilizers, anti-blocking agents, flameretardants, coupling agents, compatibilizers, plasticizers, fillers, processing aids, andcombinations thereof. The one or more additives may be combined with apolyethylene resin to form a masterbatch such that a portion or all of the additivesmay be introduced to the polymeric composition in one or more masterbatches.

[0039] The polymeric composition may include an antioxidant. Nonlimitingexamples of suitable antioxidants include phenolic antioxidants, thio-basedantioxidants, phosphate-based antioxidants, and hydrazine-based metal deactivators.Suitable phenolic antioxidants include high molecular weight hindered phenols,methyl-substituted phenol, phenols having substituents with primary or secondarycarbonyls, and multifunctional phenols such as sulfur and phosphorous-containingphenol. Representative hindered phenols include 1,3,5-trimethyl-2,4,6-tris-(3,5-di20 tert-butyl-4-hydroxybenzyl)-benzene; pentaerythrityl tetrakis-3(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate; n-octadecyl-3(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate; 4,4'-methylenebis(2,6-tert-butyl-phenol); 4,4'-thiobis(6-tert-butyl-ocresol); 2,6-di-tertbutylphenol;6-(4-hydroxyphenoxy)-2,4-bis(n-octyl-thio)-l,3,5triazine; di-n-octylthio)ethyl 3,5-di-tert-butyl-4-hydroxy-benzoate; and sorbitolhexa[3-(3,5-di-tert-butyl-4-hydroxy-phenyl)-propionate]. The polymeric compositionmay include pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), commercially available as IrganoxTM 1010 from BASF.A nonlimiting example of a suitable methyl-substituted phenol isisobutylidenebis(4,6-dimethylphenol). A nonlimiting example of a suitablehydrazine-based metal deactivator is oxalyl bis(benzylidiene hydrazide). Thepolymeric composition may contain from 0 wt%, or 0.001 wt%, or 0.01 wt%, or 0.02wt%, or 0.05 wt%, or 0.1 wt%, or 0.2 wt %, or 0.3 wt %, or 0.4 wt% to 0.5 wt%, or0.6 wt %, or 0.7 wt%, or 0.8 wt %, or 1.0 wt %, or 2.0 wt%, or 2.5 wt%, or 3.0 wt%antioxidant, based on total weight of the polymeric composition.

[0040] The composition may include a processing aid. Nonlimiting examples ofsuitable processing aids include oils, organic acids (such as stearic acid), and metalsalts of organic acids (such as zinc stearate). In an embodiment, the compositioncontains from 0 wt%, or 0.01 wt%, or 0.02 wt%, or 0.05 wt%, or 0.07 wt%, or0.1 wt%, or 0.2 wt %, or 0.3 wt %, or 0.4 wt% to 0.5 wt%, or 0.6 wt %, or 0.7 wt%,or 0.8 wt %, or 1.0 wt %, or 2.0 wt%, or 2.5 wt%, or 3.0 wt%, or 5.0 wt%, or 10.0wt%, or 20.0 wt% processing aid, based on total weight of the composition.

[0041] The composition may contain from 0 wt% or greater, or 0.001 wt% orgreater, or 0.002 wt% or greater, or 0.005 wt% or greater, or 0.006 wt% or greater, or0.008 wt% or greater, or 0.009 wt% or greater, or 0.01 wt% or greater, or 0.2 wt% orgreater, or 0.3 wt% or greater, or 0.4 wt% or greater, or 0.5 wt% or greater, or 1.0wt% or greater, or 2.0 wt% or greater, or 3.0 wt% or greater, or 4.0 wt% or greater, or5.0 wt% or greater, or 10.0 wt% or greater, or 15.0 wt% or greater, or 20.0 wt% orgreater, or 30 wt% or greater, or 40 wt% or greater, or 50 wt% or greater additive,based on the total weight of the polymeric composition.Coated Conductor

[0042] The present disclosure also provides a coated conductor. The coatedconductor includes a conductor and a coating on the conductor, the coating includingthe polymeric composition. The polymeric composition is at least partially disposedaround the conductor to produce the coated conductor. The conductor may comprisea conductive metal or an optically transparent structure.

[0043] The process for producing a coated conductor includes mixing and heatingthe polymeric composition to at least the melting temperature of the polymericcomponents in an extruder to form a polymeric melt blend, and then coating thepolymeric melt blend onto the conductor. The term "onto" includes direct contact orindirect contact between the polymeric melt blend and the conductor. The polymericmelt blend is in an extrudable state.

[0044] The polymeric composition is disposed around on and / or around theconductor to form a coating. The coating may be one or more inner layers such as aninsulating layer. The coating may wholly or partially cover or otherwise surround orencase the conductor. The coating may be the sole component surrounding theconductor. Alternatively, the coating may be one layer of a multilayer jacket or sheathencasing the conductor. The coating may directly contact the conductor. The coatingmay directly contact an insulation layer surrounding the conductor.ExamplesTest Methods

[0045] Elongation at break: Tensile testing to determine elongation at break wasconducted according to ASTM D638 at 5.08 centimeters per minute using anInternational Organization for Standards 527 type 5a dog bone using a INSTRUMETTM 4201 tensile tester. Percent retention of elongation was determined bydividing the average elongation at break of a sample after UV aging by theelongation at break of an unaged sample. The elongation at break data of Table 3is reported as the average elongation at break for five of samples with 1 standarddeviation also being reported.

[0046] Grey contrast: Percent gray contrast was calculated using ImageJ software(NIH) on a marking generated at a beam wavelength of 1064.6 nm, a frequency of60 kHz, an intensity of 90% and a marking speed of 2000 mm / s.

[0047] Molecular Weight: Unless otherwise denoted herein, molecular weight isthe weight average molecular weight and is determined by Gel PermeationChromatography. Gel permeation chromatography (GPC) was performed on aWaters modular chromatographic HPLC / SEC system. The mobile phase wastetrahydrofuran with 0.08 molar diethanolamine and was degassed with helium.Two mesopore columns from Polymer Laboratories were used. The GPC wasperformed at a temperature of 30° C and a flow rate of 0.6 liters per minute. Theconcentration used was greater than 10 milligrams per milliliter and the injectionvolume was 50 microliters. The GPC measurement was carried out for a timeperiod of 40 minutes. Calibration for the GPC was carried out using a polynomialof degree 3 based on 8 polystyrene standards with a narrow molecular weightdistribution with peak molecular weight of between 382 g / mol and 95000 g / mol.Materials

[0048] The materials used in the examples are provided below.

[0049] Resin is a UNIPOLTM gas phase unimodal medium density polyethylenewith a density of 0.935 g / cc and a melt index (MI, I2) of 0.6 g / 10 min (190°C. / 2.16 kg).

[0050] CBMB is a carbon black masterbatch that is 45 wt% carbon black and isavailable from The Dow Chemical Company, Midland, MI, USA.

[0051] HALS is a hindered amine light stabilizer having a CAS registrationnumber of 70624-18-9 and is commercially available under the tradenameCHIMASSORBTM 944 from BASF, Ludwigshafen, Germany.

[0052] HA10 is a polymeric ultraviolet light stabilizer having a CAS registrationnumber of 136504-96-6 and a weight average molecular weight of approximately10,000 as measured according to Gel Permeation Chromatography. HA10 iscommercially available under the tradename UVASORBTM HA10 from 3V SigmaUSA, Georgetown, South Carolina, USA.

[0053] HA88 is an oligomeric ultraviolet light stabilizer having a CAS registrationnumber of 136504-96-6 and a weight average molecular weight of approximately3,000 as measured according to Gel Permeation Chromatography. HA88 iscommercially available under the tradename UVASORBTM HA88 from 3V SigmaUSA, Georgetown, South Carolina, USA.

[0054] AO is poly(1,2-dihydro-2,2,4-trimethylquinoline) having a CAS registrationnumber of 26780-96-1 and commercially available under the tradenameNAUGARDTM Super Q stabilizer from Addivant, Danbury, Connecticut, USA.

[0055] PA is a fluororesin processing aid commercially available under thetradename DYNAMARTM FX 5912 available from 3M, Saint Paul, Minnesota, USA.

[0056] Resin 2: is a UNIPOLTM gas phase unimodal high-density polyethylenewith a density of 0.945 g / cc and a melt index (MI, I2) of 0.8 g / 10 min (190°C. / 2.16 kg).Sample Preparation

[0057] Inventive examples ("IE"), comparative examples ("CE") and test samples(S) were prepared on a BRABENDERTM 10 mixer preheated to 180°C and mixed atrevolutions per minute ("rpm") with roller blades. First, all resins were addedand brought to a flux. Stabilizers and process aids were then added and fluxed forminutes. The examples and test samples were then cold pressed, coarsepelletized, and extruded on a BRABENDERTM extruder. The temperature profileof the extruder was 150°C to 180°C, 40 rpm, and a 20 / 40 / 20 screen pack. Thestrand was then pelletized to form pellets.

[0058] Plaques were prepared by compression molding pellets on a pre-heatedArbor press to 180°C. The pellets were placed into a 1.905 millimeter (mm) mold.The samples were heated to 180°C for 4 minutes, then pressed for 3 minutes at apressure 3.45 MPa followed by 3 minutes at a pressure of 17.24 MPa. Sampleswere cooled in the press at 15°C per minute until reaching approximately 23°Cand then conditioned per testing requirements. Dog bone specimens were cutfrom the compression molded plaques.

[0059] Ultraviolet aging was performed on the dog bone samples according toTelecordia GR-20 with cycles at 70°C at 0.7 W / (m2nm) irradiation for 20 hoursfollowed by 4 hours of dark condensation at 55°C. Samples were pulled at 1000hour and 2000 hour increments.

[0060] Compression molded plaques (1.27 mm X 101.6 mm X 101.6 mm) of thetest samples were prepared and laser marked according to the parameters of Table1.Table 1

[0061] Table 2 provides the composition and grey contrast of the test samples. Thepurpose of the test samples was to demonstrate grey contrast as a function of carbonblack concentration. The CBMB values of Table 2 provide the weight percent, basedon the total weight of the test sample, of the CBMB and in parentheses the carbonblack weight percent.Table 2

[0062] As can be seen from Table 2, test samples 1 and 2 both have sufficiently lowcarbon black levels to enable a grey contrast of greater than 25%. As such, testsamples 1 and 2 are laser printable. Testing samples S3-S6 exhibit grey contrasts of25% or less meaning that the compositions with carbon black weight percent of 0.38and greater are not laser printable.

[0063] Table 3 provides the composition of IE1-IE4 and CE1-CE3. Table 3 alsoprovides the mechanical testing data for the initial state (i.e., no accelerated UVaging) and UV aged states after 1000 hours ("h') or 2000 hours of accelerated UVexposure.Table 3

[0064] As can be seen from Table 3, IE1-IE4 all have carbon black concentrationssufficiently low enough to enable laser printing and as such it is believed that IE1-IE4are laser printable. Further, IE1-IE4 all retain 50% or more elongation at break after2000 hours of accelerated ultraviolet exposure. IE1 demonstrates that the use of thepolymeric stabilizer, without additional oligomeric stabilizers, may allow for theformation of a laser printable composition that retains 50% or more of its elongationat break after 2000 hours of accelerated ultraviolet exposure. IE2-IE4 eachdemonstrate that oligomeric stabilizers of the same or different type as the polymericstabilizer may be utilized in addition to the polymeric stabilizer and still enable a laserprintable composition that retains 50% or more of its elongation at break after 2000hours of accelerated ultraviolet exposure. CE1, with 2.55 wt% carbon black,unsurprisingly retains 50% or more of its elongation at break after 2000 hours ofaccelerated ultraviolet exposure but is not laser printable based on theunderstanding provided by Table 2. CE2 and CE3 demonstrate that without thepolymeric stabilizer the compositions may be laser printable due to low carbonblack levels but cannot retain 50% or more of its elongation at break after 2000hours of accelerated ultraviolet exposure.

Claims

1. A polymeric composition comprising: an ethylene polymer; 0.05 wt% to 0.25 wt% carbon black based on a total weight of the polymeric composition; and a polymeric ultraviolet light stabilizer comprising a hindered amine moiety and having a weight average molecular weight from 5,000 g / mol to 20,000 g / mol as measured according to Gel Permeation Chromatography.

2. The polymeric composition of claim 1, wherein the polymeric composition comprises 95 wt% or greater of the ethylene polymer based on a total weight of the polymeric composition.

3. The polymeric composition of any one of claims 1 and 2, wherein the ethylene polymer has a density of from 0.919 g / cc to 0.950 g / cc as measured by ASTM D792.

4. The polymeric composition of any one of claims 1-3, wherein the polymeric composition further comprises: an oligomer ultraviolet light stabilizer having a weight average molecular weight of from 1,000 g / mol to 5,000 g / mol as measured according to Gel Permeation Chromatography.

5. The polymeric composition of claim 4, wherein the polymeric composition comprises from 0.25 wt% to 1.0 wt% of the oligomer ultraviolet light stabilizer based on a total weight of the polymeric composition.

6. The polymeric composition of any one of claims 1-5, wherein the oligomer ultraviolet light stabilizer has a chemical abstract services registration number of7. The polymeric composition of any one of claims 1-6, wherein the polymeric composition comprises from 0.10 wt% to 0.25 wt% carbon black based on a total weight of the polymeric composition.

8. The polymeric composition of any one of claims 1-7, wherein the polymeric composition comprises from 0.25 wt% to 2 wt% of the polymeric ultraviolet light stabilizer based on a total weight of the polymeric composition.

9. The polymeric composition of any one of claims 1-8, wherein the polymeric ultraviolet light stabilizer has a weight average molecular weight from 8,000 g / mol to 12,000 g / mol as measured according to Gel Permeation Chromatography, further wherein the polymeric ultraviolet light stabilizer has a chemical abstract services registration number of 136504-96-6.

10. A coated conductor comprising: a conductor; and the polymeric composition of any one of claims 1-9 disposed at least partially around the conductor.