Polymeric compositions comprising polylactic and methods of making and using same

Technical Field [0001] The disclosure relates to polymer compositions. More specifically, the present disclosure relates to polymer compositions comprising a biodegradable polymer.

Background [0002] Synthetic polymeric substances, such as polypropylene and polyethylene resins, are widely used in the production of various end products from medical devices to food containers. Many industries, such as the packaging industry, use polypropylene substances in various manufacturing processes to obtain various end products, including bicomponent fibers and multilayer films.

[0003] While products made of synthetic polymer substances find widespread use, one disadvantage of their use is that these substances tend to be semi-solid in the environment. In response to environmental issues, interest in the production and use of readily biodegradable polymer substances is increasing. These substances, also known as 'organic substances', may undergo accelerated degradation in the environment. The use of these biodegradable polymeric substances is often limited by their poor mechanical and / or physical properties. Thus, there is a need to develop biodegradable polymer compositions having the desired physical and / or mechanical properties.

SUMMARY [0004] The present specification discloses a multi-component article comprising a first component comprising a biodegradable polymer and a second component consisting of a polyolefin and a reactive modifying agent, wherein the reactive modifying agent is an epoxy functional polyolefin.

[0005] The present specification also discloses a method of producing a multilayer film comprising coextruding the first and second layers of the film, the first layer comprising polylactic acid and the second layer consisting of polyolefin and polyolefin with epoxy functional groups.

[0006] In addition, the present specification discloses a method of producing a multi-component fiber comprising coextruding a core component and a shell component, wherein the core component consists of polyolefin and polyolefin with epoxy functional groups, and the shell component comprises polylactic acid.

BRIEF DESCRIPTION OF THE DRAWINGS [0007] For a more complete understanding of the present disclosure and its advantages, reference is made to the following brief description together with the accompanying drawing and a detailed description in which similar reference numerals denote similar parts.

[0008] Figure 1 shows illustrations of bicomponent fibers.

[0009] Figure 2 shows illustrations of multi-layer films.

[0010] Figures 3 and 4 show Fourier transform infrared spectroscopy (FTIR) spectra for the samples of Example 1.

DETAILED DESCRIPTION [0011] It should be understood initially that, despite providing the following illustrative embodiment of one or more forms, the disclosed systems and / or methods can be implemented using any number of techniques, both currently known and existing. The disclosure should in no way be limited to illustrative embodiments, drawings and techniques illustrated below, including exemplary designs and embodiments illustrated and described herein, but may be modified within the scope of the appended claims together with the full range of their equivalents.

[0012] Disclosed herein are multi-component articles in which at least one component comprises a biodegradable polymer and at least one component includes polyolefin and a reactive modifying agent. In this specification, the term biodegradable refers to substances that can be broken down in particular to obtain harmless products through the action of living organisms. According to one embodiment, the multi-component article may contain additional components, wherein the component comprising polyolefin and reactive modifier is positioned so that the individual components adhere to each other. According to an embodiment, the biodegradable polymer comprises polylactic acid (PLA) and the multi-component article comprises at least one component comprising PLA and at least one component comprising polyolefin and a reactive modifying agent. The various components of the multi-component article are described in more detail later in this description. Multi-component devices of the type described herein may exhibit the desired physical and / or mechanical properties compared to those consisting of polyolefin or polylactic acid alone or having at least one component comprising polyolefin, at least one component comprising a biodegradable polymer and no reactive component modifying agent.

[0013] A multi-component article may comprise at least one component comprising a polyolefin. According to an embodiment, the polyolefin is polypropylene. In an alternative embodiment, the polyolefin is polyethylene.

[0014] According to an embodiment, the polyolefin is polypropylene. Polypropylene may be a homopolymer provided, however, that the homopolymer contains up to 5% of another alpha-olefin, including but not limited to C2-C8 alpha-olefins such as ethylene and 1-butene. Despite the potential presence of small amounts of other alpha-olefins, polypropylene is generally referred to as polypropylene homopolymer.

[0015] According to an embodiment, the polypropylene homopolymer is present in the component component of the article in an amount of from 1 weight percent (wt%) to 99 wt% based on the total weight of the multi-component article, alternatively from 5 wt. up to 70% by weight, alternatively from 10% by weight up to 50 wt.

[0016] Polypropylene homopolymers suitable for use in the context of the present disclosure may include any type of polypropylene known in the art with the help of the present disclosure. For example, the polypropylene homopolymer may be atactic polypropylene, isotactic polypropylene, hemi-isotactic, syndiotactic polypropylene or combinations thereof. A polymer is "atactic" when its side groups are located randomly on both sides of the polymer chain. In contrast, a polymer is "isotactic" when all its side groups are located on the same side of the chain and "syndiotactic" when its side groups are alternately on opposite sides of the chain. In the hemiisotactic polymer, each other repetitive has a random substituent.

[0017] According to an embodiment, the polypropylene suitable for use in accordance with the present disclosure may have a density of 0.895 g / cm³ up to 0.920 g / cm³, alternatively from 0.900 g / cm³ up to 0.915 g / cm³ and alternatively from 0.905 g / cm³ up to 0.915 g / cm³ determined in accordance with ASTM D1505; and a melting point from 150 ° C to 170 ° C, alternatively from 155 ° C to 168 ° C and alternatively from 160 ° C to 165 ° C determined by differential scanning calorimetry; melt flow rate from 0.5 g / 10 min to 30 g / 10 min, alternatively from 1.0 g / 10 min to 15 g / 10 min, and alternatively from 1.5 g / 10 min to 5.0 g / 10 min specified in ASTM D1238 condition "L"; tensile modulus from 200,000 psi to 350,000 psi; alternatively from 220,000 psi to 320,000 psi and alternatively from 250,000 psi to 320,000 psi determined according to ASTM D638; stretching at the yield strength from 3,000 psi to 6,000 psi, alternatively from 3,500 psi to 5,500 psi and alternatively from 4,000 psi to 5,500 psi determined according to ASTM D638; yield stress elongation from 5% to 30%, alternatively from 5% to 20% and alternatively from 5% to 15% determined in accordance with ASTM D638; flexural modulus from 120,000 psi to 330,000 psi, alternatively 190,000 psi to 310,000 psi and alternatively 220,000 psi to 300,000 psi determined according to ASTM D790; Gardner impact strength from 3 pounds per inch to 50 pounds per inch, alternatively from 5 pounds per inch to 30 pounds per inch and alternatively from 9 pounds per inch to 25 pounds per inch determined in accordance with ASTM D2463; impact strength from 0.2 foot-pounds / inch to 20 foot-pounds / inch, alternatively from 0.5 foot-pounds / inch to 15 foot-pounds / inch and alternatively from 0.5 foot-pounds / inch to 10 foot-pounds / inch determined in accordance with ASTM D256A ; Shora D hardness from 30 to 90, alternatively from 50 to 85 and alternatively from 60 to 80 determined in accordance with ASTM D2240 and a deflection temperature under load from 50 ° C to 125 ° C, alternatively from 80 ° C to 115 ° C and alternatively from 90 ° C to 110 ° C determined according to ASTM D648.

[0018] Examples of polypropylene homopolymers suitable for use in accordance with the present disclosure include without limitation 3371, 3271, 3270 and 3276, which are commercially available polypropylene homopolymers from Total Petrochemicals USA, Inc. According to an embodiment, the polypropylene homopolymer (e.g. 3371) has the physical properties given in Table 1. Table 1

<td>properties</td><td>Typical value 3371</td><td>Test method</td>

<td colspan="3">physical</td>

<td>₃Density, g / cm</td><td> 0,905</td><td>ASTM D1505</td>

<td>Melt flow rate (MFR), g / 10 min</td><td> 2,8</td><td>ASTM D1238 condition 'L'</td>

<td colspan="3">mechanical</td>

<td>Tensile modulus, psi</td><td> 235,000</td><td>ASTM D638</td>

<td>Tensile strength at the yield point, psi</td><td> 5,100</td><td>ASTM D638</td>

<td>Elongation at yield point,%</td><td> 7,5</td><td>ASTM D638</td>

<td>Flexural modulus, psi</td><td> 202,000</td><td>ASTM D790</td>

<td colspan="3">toughness</td>

<td>Impact strength according to Gardner, pounds per inch</td><td> 149,2</td><td>ASTM D2463</td>

<td>Impact strength Izod, foot-pounds / inches</td><td> 0,69</td><td>ASTM D256A</td>

<td colspan="3">hardness</td>

<td>Shora hardness D</td><td> 75</td><td>ASTM D2240</td>

<td colspan="3">thermal</td>

<td>Deflection temperature under load, ° F</td><td> 207</td><td>ASTM D648</td>

<td>Melting point (DSC), ° F</td><td> 325</td><td>DSC</td>

[0019] According to another embodiment, the polypropylene may be a high crystallinity polypropylene homopolymer (HCPP). HCPP may contain mainly isotactic polypropylene. The isotacticity of polymers can be measured by spectroscopy¹³C NMR using meso pentadas and can be expressed as a percentage of meso pentadas (% mmmm). The term "meso pentads" as used herein refers to successive methyl groups on the same side of the polymer chain. According to an embodiment, HCPP has a meso pentad percentage greater than 97% or greater than 98% or greater than 99%. HCPP may include some amount of atactic or amorphous polymer. The atactic part of the polymer is xylene soluble and is therefore called xylene soluble fraction (XS%). When determining XS%, the polymer dissolves in boiling xylene, and then the solution is cooled to 0 ° C resulting in precipitation of the isotactic or crystalline portion of the polymer. XS% is that part of the original quantity that remains soluble in cold xylene. Thus, XS% in the polymer is an indicator of the degree of crystalline polymer formed. The total amount of polymer (100%) is the sum of the xylene soluble fraction and xylene insoluble fraction, determined in accordance with ASTM D5492-98. According to an embodiment, the HCPP has a xylene soluble fraction of less than 1.5% or less than 1.0% or less than 0.5%.

[0020] According to an embodiment, an HCPP suitable for use in accordance with the present disclosure may have a density of 0.895 g / cm³ up to 0.920 g / cm³, alternatively from 0.900 g / cm³ up to 0.915 g / cm³ and alternatively from 0.905 g / cm³ up to 0.915 g / cm³ determined in accordance with ASTM D1505; melt flow rate from 0.5 g / 10 min to 30 g / 10 min, alternatively from 1.0 g / 10 min to 15 g / 10 min and alternatively from 1.5 g / 10 min to 5.0 g / 10 min determined in accordance with ASTM D1238; secant module in the machine direction (MD) from 350,000 psi to 420,000 psi; alternatively from 380,000 psi to 420,000 psi and alternatively from 400,000 psi to 420,000 psi determined according to ASTM D882; transverse secant module (TD) from 400,000 psi to 700,000 psi, alternatively from 500,000 psi to 700,000 psi and alternatively from 600,000 psi to

700,000 psi determined according to ASTM D882; tensile strength at break in MD direction from 19,000 psi to 28,000 psi, alternatively from 22,000 psi to 28,000 psi and alternatively from 25,000 psi to 28,000 psi determined according to ASTM D882; tensile strength at break in TD direction from 20,000 psi to 40,000 psi, alternatively from 30,000 psi to 40,000 psi and alternatively from 35,000 psi to 40,000 psi determined according to ASTM D882; elongation at break in the MD direction from 50% to 200%, alternatively from 100% to 180% and alternatively from

120% to 150% determined in accordance with ASTM D882; elongation at break in TD direction from 50% to 150%, alternatively 60% to 100% and alternatively 80% to 100% determined in accordance with ASTM D882; melting point from 150 ° C to 170 ° C, alternatively from 155 ° C to 170 ° C and alternatively from 160 ° C to 170 ° C determined by differential scanning calorimetry; gloss at 45 ° from 70 to 95, alternatively 75 to 90 and alternatively 80 to 90 determined in accordance with ASTM D2457; turbidity percentage from 0.5% to 2.0%, alternatively from 0.5% to 1.5% and alternatively from 0.5% to 1.0% determined in accordance with ASTM D1003 and water vapor transmission rate from 0.15 up to 0.30 g-mil / 100 inches²/ day, alternatively 0.15 to 0.25 g-mil / 100 inches²/ day and alternatively from 0.20 to 0.21 g-mil / 100 inches²/ day determined in accordance with ASTM F-1249-90.

[0021] An example of an HCPP suitable for use in accordance with the present disclosure includes without limitation 3270, which is HCPP commercially available from Total Petrochemicals USA, Inc. HCPP (e.g. 3270) may have the general physical properties shown in Table 2.

Table 2

<td>properties</td><td>Typical value 3270</td><td>Test method</td>

<td>physical</td><td></td><td></td>

<td>₃Density, g / cm</td><td> 0,910</td><td>ASTM D1505</td>

<td>Melt mass flow rate (MFR) (230 ° C / 2.16kg), g / 10 min</td><td> 2,0</td><td>ASTM D1238</td>

<td colspan="3">Mechanical BOPP</td>

<td>Secant module MD, psi</td><td> 420,000</td><td>ASTM 882</td>

<td>Secant module TD, psi</td><td> 700,000</td><td>ASTM 882</td>

<td>Tensile strength at break MD, psi</td><td> 28,000</td><td>ASTM 882</td>

<td>Tensile strength at break TD, psi</td><td> 39,000</td><td>ASTM 882</td>

<td>Elongation at break MD,%</td><td> 150</td><td>ASTM 882</td>

<td>Elongation at break TD,%</td><td> 60</td><td>ASTM 882</td>

<td colspan="3">thermal</td>

<td>Melting point, ° F</td><td> 329</td><td>DSC</td>

<td colspan="3">optical</td>

<td>Gloss (45 °)</td><td> 85</td><td>ASTM D2457</td>

<td>Turbidity,%</td><td> 1,0</td><td>ASTM D1003</td>

<td colspan="3">Barrier</td>

<td>Water vapor transmission rate, 100 ° F, 90% humidity resp., gmil / 100 inches²/ day</td><td> 0,2</td><td>ASTM F1249-90</td>

[0022] According to another embodiment, the polypropylene may be a polypropylene copolymer, for example a heterophasic polypropylene copolymer (PPHC), also known as a polypropylene percussion copolymer, wherein the polypropylene phase or homopolymer component is attached to the copolymer component or phase. PPHC may comprise from more than 6.5 wt. to less than

11.5 wt. ethylene based on the total weight of PPHC, alternatively from 8.5 wt. to less than

10.5% by weight, alternatively from 9.5% by weight

[0023] The PPHC copolymer phase may be a random copolymer of propylene and ethylene, also called ethylene / propylene rubber (EPR). Heterophasic PP copolymers exhibit pronounced homopolymer phases that are interrupted by short sequences or blocks with random ethylene and propylene alignment. Compared with random copolymers, block segments including EPR may exhibit some polymeric properties (e.g., intrinsic viscosity) that are different from those of the copolymer as a whole. Without wishing to be limited to theory, part of the EPR PPHC has rubber properties that, when incorporated into the matrix, the homopolymer component, can be used to provide increased PPHC impact resistance. According to an embodiment, the EPR part of PPHC comprises more than 14 wt. PPHC, alternatively more than 18 wt. PPHC, alternatively from 14 wt. up to 18 wt. PPHC.

[0024] The amount of ethylene present in the EPR PPHC portion may be from 38 wt. up to 50% by weight, alternatively from 40% by weight up to 45% by weight relative to the total weight of the EPR part. The amount of ethylene present in the EPR part of PPHC can be determined spectrophotometrically using Fourier transform infrared spectroscopy (FTIR). Specifically, the FTIR spectrum of the polymer sample is recorded for a series of samples with known ethylene content in EPR. Transmittance ratio at 720 cm^-1/ 900cm^-1 is calculated for each ethylene concentration and then a calibration curve can be created. Linear regression analysis can then be performed on the calibration curve to derive the equation used then to determine the ethylene content of the EPR for the sample substance.

[0025] The EPR part of PPHC may have an internal viscosity different from the propylene homopolymer component. In the present specification, internal viscosity refers to the ability of the polymer in solution to increase the viscosity of this solution. Viscosity is herein referred to as flow resistance due to internal friction. According to an embodiment, the intrinsic viscosity of the EPR PPHC portion may be greater than 2.0 dl / g, alternatively 2.0 dl / g to 3.0 dl / g, alternatively 2.4 dl / g to 3.0 dl / g, alternatively from 2.4 dl / g to 2.7 dl / g, alternatively from 2.6 dl / g to 2.8 dl / g. The internal viscosity of the EPR PPHC part is determined according to ASTM D5225. [0026] According to an embodiment, PPHC may have a melt flow index (MFR) from 65 g / 10 min to 130 g / 10 min, alternatively from 70 g / 10 min to 120 g / 10 min, alternatively from 70 g / 10 min to 100 g / 10 min, alternatively from 70 g / 10 min to 90 g / 10 min, alternatively from 75 g / 10 min to 85 g / 10 min, alternatively 90 g / 10 min. The excellent flow properties, as indicated by the high MFR, allow high throughput production of molded polymer components. According to an embodiment, PPHC is an unreacted reactor resin which can also be referred to as low order PP. According to some embodiments, PPHC is a rheology-controlled resin in which the melt flow index has been adapted by various techniques such as pre-cracking. For example, MFR can be increased by pre-cracking as described in US Patent No. 6,503,990, which is cited in its entirety as a literature source. As described in this publication, certain amounts of peroxide are mixed with the polymer resin in the form of flakes, powder or pellets to increase the MFR of the resin. The MFR as used herein denotes the amount of molten polymer resin that will flow through the orifice at a given temperature and load. The MFR can be determined using a supportive piston plastometer that extruds polypropylene through a defined hole at 230 ° C and a load of 2.16 kg in accordance with ASTM D1238.

[0027] Representative examples of suitable PPHCs include, without limitation, 4920W and 4920WZ, which are commercially available copolymer impact resins from Total Petrochemicals USA Inc. According to an embodiment, PPHC (e.g. 4920W) has the general physical properties shown in Table 3.

Table 3

<td>properties</td><td>Typical value</td><td>Method ASTM</td>

<td colspan="3">Physical (resin)</td>

<td>Flow rate, g / 10 min.</td><td> 100</td><td>D1238</td>

<td>Density, g / cm³</td><td> 0,905</td><td>D1505</td>

<td>Melting point, ° C</td><td> 160-165</td><td>DSC</td>

<td colspan="3">mechanical</td>

<td>Tensile strength at the yield point, psi (MPa)</td><td> 3700 (25)</td><td>D638</td>

<td>Elongation at yield point,%</td><td> 6</td><td>D638</td>

<td>Flexural modulus, psi (MPa)</td><td> 190,000 (1,300)</td><td>D790</td>

<td>Impact strength, foot-pounds / inches (J / m)</td><td> 1,0(50)</td><td>ASTM D256A</td>

<td colspan="3">thermal</td>

<td>Thermal deflection, ° C</td><td> 90</td><td>D648</td>

[0028] According to an embodiment, the polyolefin is polyethylene, alternatively high density polyethylene, alternatively low density polyethylene, alternatively low density linear polyethylene.

[0029] According to an embodiment, polyethylene is present in the component in an amount of from 1 wt. up to 99 wt. based on the total weight of the multi-component article, alternatively from 5 wt. up to 70% by weight, alternatively from 10% by weight up to 50 wt.

[0030] According to an embodiment, the polyolefin comprises high density polyethylene (HDPE). IN₃ here, HDPE has a density equal to or greater than 0.941 g / cm³, alternatively from

0.941 g / cm³ up to 0.965 g / cm³, alternatively from 0.945 g / cm³ up to 0.960 g / cm³. The HDPE may be a homopolymer or copolymer, For example a copolymer of ethylene with one or more alpha-olefin monomers such as propylene, butene, hexene, etc. According to a certain form,

HDPE is a homopolymer. An HDPE suitable for use in accordance with the present disclosure may generally have a certain melt flow rate as determined in accordance with

ASTM D1238, from 0.01 g / 10 min to 50 g / 10 min or from 0.5 g / 10 min to 20 g / 10 min or from 1.0 g / 10 min to 10 g / 10 min. According to an embodiment, HDPE suitable for use in accordance with the present disclosure may generally have a tensile modulus, determined in accordance with ASTM D638, from 100,000 psi to 350,000 psi or from 150,000 psi to 300,000 psi or from 180,000 psi to 220,000 psi. According to an embodiment, the HDPE suitable for use in accordance with the present disclosure may generally have a flexural modulus, defined ASTM D790, from 30,000 psi to 350,000 psi or from 100,000 psi to 300,000 psi or from 150,000 psi to 200,000 psi. According to an embodiment, HDPE suitable for use in accordance with the present disclosure may generally have a melting point, determined by differential scanning calorimetry (DSC), 120 ° C to 140 ° C or 125 ° C to 135 ° C or 130 ° C up to 133 ° C.

[0031] Examples of HDPE suitable for use in accordance with the present disclosure include without limitation 6450 HDPE, which is a polyethylene resin and mPE ER 2283 POLYETHYLENE, which is a high density metallocene polyethylene resin with hexene as comonomer, both commercially available from Total Petrochemicals USA, Inc. According to an embodiment, the respective HDPE generally has the physical properties shown in Table 4 (e.g., 6450 HDEP) or Table 5 (e.g., ER 2283).

Table 4

<td>properties</td><td>Typical value</td><td>ASTM method</td>

<td colspan="3">Resin⁽¹⁾</td>

<td>Melt flow rate 190 ° C / 2.16 kg, g / 10 min</td><td> 5,0</td><td>D 1238</td>

<td>₃Density, g / cm</td><td> 0,962</td><td>D 792</td>

<td>Melting point, ° F</td><td> 265</td><td>D 3417</td>

<td>Foil⁽¹⁾⁽²⁾</td><td></td><td></td>

<td colspan="3">Turbidity,%</td>

<td>Gloss,%</td><td> 85</td><td>D 523</td>

<td>Tensile strength at break (MD), psi</td><td> 3500</td><td>D 882</td>

<td>Tensile strength at break (TD), psi</td><td> 3800</td><td>D 882</td>

<td>Elongation at break (MD),%</td><td> 850</td><td>D 882</td>

<td>Elongation at break (TD),%</td><td> 650</td><td>D 882</td>

<td>Secant module at 2% stress (MD), psi</td><td> 100,000</td><td>D 882</td>

<td>Secant module at 2% stress (TD), psi</td><td> 130,000</td><td>D 882</td>

<td>WTR⁽³⁾ at 100 ° F, g / 100 inches²/ day</td><td> 0,5</td><td>E 96/66</td>

<td>Fragility at low temperatures, ° F</td><td> &lt;-112</td><td>D 746</td>

<td colspan="3">⁽¹⁾ The data were obtained in laboratory conditions and are not intended to be used as specifications, maximum or minimum values.⁽²⁾ Data given was for 1.0 mil film cast.⁽³⁾ Water vapor transmission rate.</td>

Table 5

<td>properties</td><td>Method</td><td>units</td><td>Value</td>

<td colspan="4">physical</td>

<td>Density</td><td>ISO 1183</td><td>g / cm³</td><td> 0.950</td>

<td>Melting index (2.16 kg)</td><td>ISO 1133</td><td>g / 10 min</td><td> 2.0</td>

<td>Melting temperature</td><td>EN ISO 11357</td><td>° C</td><td> 133</td>

<td>Vicat temperature</td><td>ISO 306</td><td>° C</td><td> 130</td>

<td colspan="4">Cast foil</td>

<td>Impact measurement using the falling element method</td><td>ISO 7765-1</td><td>g</td><td> 36</td>

<td>Tensile strength at the MD / TD yield point</td><td>ISO 527-3</td><td>MPa</td><td> 23/24</td>

<td>Tensile strength at break MD / TD</td><td>ISO 527-3</td><td>MPa</td><td> 43/41</td>

<td>Elongation at break MD / TD</td><td>ISO 527-3</td><td> %</td><td> 640/820</td>

<td>Elmendorf MD / TD test</td><td>ISO 6393</td><td>N / mm</td><td> 8/130</td>

<td>turbidity</td><td>ISO 14782</td><td> %</td><td> 10</td>

<td>Gloss 45 °</td><td>ASTM D 2457</td><td></td><td> 68</td>

[0032] According to an embodiment, the polyolefin comprises low density polyethylene (LDPE). In this specification, LDPE is defined as having a density in the range of 0.910 g / cm³ down

0.940 g / cm³, alternatively from 0.917 g / cm³ up to 0.935 g / cm³ and alternatively from 0.920 g / cm³ to 0.930 ₃ g / cm³. LDPE can be additionally characterized by the presence of an increased number of branches compared to HDPE. The LDPE may be a homopolymer or copolymer, for example a copolymer of ethylene with one or more alpha-olefin monomers such as propylene, butene, hexene, etc. In an embodiment, LDPE is a homopolymer. LDPE suitable for use in accordance with the present disclosure may generally have a molten mass flow rate, as determined by ASTM D1238, from 0.1 g / 10 min to 60 g / 10 min or from 0.5 g / 10 min to 30 g / 10 min or from 1 g / 10 min to 20 g / 10 min. According to an embodiment, an LDPE suitable for use in accordance with the present disclosure may generally have a tensile modulus, defined ASTM D638, from 10,000 psi to 70,000 psi or from 15,000 psi to 65,000 psi or from 20,000 psi to 60,000 psi. According to an embodiment, an LDPE suitable for use in accordance with the present disclosure may generally have a flexural modulus, defined ASTM D790, from 9,000 psi to 60,000 psi or from 10,000 psi to 55,000 psi or from 15,000 psi to 50,000 psi. According to an embodiment, an LDPE suitable for use in accordance with the present disclosure may generally have a melting point, determined by differential scanning calorimetry (DSC), from 85 ° C to 125 ° C or from 90 ° C to 120 ° C or from 95 ° C up to 120 ° C.

[0033] A representative example of a suitable LDPE is 1020 FN 24, which is LDPE commercially available from Total Petrochemicals USA, Inc. LDPE (e.g. 1020 FN 24) may generally have the physical properties shown in Table 6.

Table 6

<td></td><td>English</td><td>SI</td><td>Method</td>

<td colspan="4">Nominal Resin Properties</td>

<td>Density</td><td> -</td><td>0.922 g / cm³</td><td>ASTMD1505</td>

<td>Melting index, 190 ° C / 2.16 Kg</td><td> -</td><td>2.1 g / 10min</td><td>ASTM D1238</td>

<td>Melting temperature</td><td>232 ° F</td><td>109 ° C</td><td>ASTMD3418</td>

<td>Vicat softening temperature</td><td>209 ° F</td><td>94 ° C</td><td>ASTM D1525</td>

<td colspan="4">Nominal Properties of Blown Film at 40um⁽¹⁾</td>

<td>turbidity</td><td> 7,0%</td><td> 7,0%</td><td>ASTM D1003</td>

<td>Tensile strength at the yield point MD / TD</td><td>1595psi / 1523psi</td><td>11MP / 10,5MPa</td><td>ISO 527-3</td>

<td>Tensile strength at break MD / TD</td><td>4061psi / 3190psi</td><td>28 / 22MPa</td><td>ISO 527-3</td>

<td>Elongation at break MD / TD</td><td> 360%/630%</td><td> 360%/630%</td><td>ISO 527-3</td>

<td>Elmendorf MD / TD test</td><td> -</td><td>75 / 45N / mm</td><td>ISO 6383-2</td>

<td>Impact measurement by method falling element</td><td> -</td><td>120g</td><td>ISO 7765-1</td>

<td>turbidity</td><td> 7%</td><td> 7%</td><td>ISO 14782</td>

<td colspan="4">⁽¹⁾ Data obtained using laboratory test samples produced under the following extrusion conditions: screw diameter 45 mm, L / D = 30, die diameter = 120 mm, die hole = 1.4 mm, BUR = 2.5: 1, temperature = 185 ° C.</td>

[0034] According to an embodiment, the polyolefin comprises low density linear polyethylene (LLDPE). LLDPE is essentially linear polyethylene, with a significant number of short branches. LLDPE is usually produced by copolymerizing ethylene with long-chain olefins.

LLDPE is structurally different from low density polyethylene due to the lack of long chain branching. According to an embodiment, the LLDPE is a copolymer, for example a copolymer of ethylene with one or more alpha-olefin monomers such as propylene, butene, hexene, etc. LLDPE suitable for use in accordance with the present disclosure may generally have a density, as determined by ASTM D792, from 0.900 g / cm³ up to 0.920 g / cm³ or from 0.905 g / cm³ up to 0.918 g / cm³ or from 0.910 g / cm³ up to 0.918 g / cm³. According to an embodiment, LLDPE suitable for use in accordance with the present disclosure may generally have a molten mass flow rate, as determined by ASTM D1238, from 0.1 g / 10 min to 50 g / min or from 0.5 g / 10 min to 30 g / 10 min or from 1 g / 10 min to 20 g / 10 min. According to an embodiment, the LLDPE suitable for use in accordance with the present disclosure may generally have a tensile modulus, defined ASTM D638, from 20,000 psi to 250,000 psi or from 50,000 psi to 220,000 psi or from 100,000 psi to 200,000 psi. In an embodiment, the LLDPE suitable for use in accordance with the present disclosure may generally have a flexural modulus, as determined by ASTM D790, from 5,000 psi to 150,000 psi or from 10,000 psi to 130,000 psi or from 50,000 psi to 110,000 psi. In an embodiment, the LLDPE suitable for use in accordance with the present disclosure may generally have a melting point, determined by differential scanning calorimetry (DSC), from 70 ° C to 140 ° C or from 80 ° C to 130 ° C or from 90 ° C up to 120 ° C.

[0035] A representative example of a suitable LLDPE is FINATHENE LL 4010 FE 18, which is LLDPE commercially available from Total Petrochemicals. LLDPE (e.g. FINATHENE LL 4010

FE 18) may generally have physical properties as shown in Table 7.

Table 7

<td></td><td>English</td><td>SI</td><td>Method</td>

<td colspan="4">Nominal Resin Properties</td>

<td>Density</td><td> -</td><td>0.918 g / cm³</td><td>ASTM D792</td>

<td>Melting index</td><td> -</td><td>1.0 g / 10min</td><td>ASTMD1238</td>

<td colspan="4">Nominal Film Properties at 0.984 mils (25um)</td>

<td>Tensile strength of the film at the yield point, MD</td><td>1600 psi</td><td>11.0 MPa</td><td>ISO 527</td>

<td>Tensile strength of the film at the yield point, TD</td><td>1600 psi</td><td>11.0 MPa</td><td>ISO 527</td>

<td>Elongation of film at break, MD</td><td> 600%</td><td> 600%</td><td>ISO 527</td>

<td>Elongation of the film at break, TD</td><td> 750%</td><td> 750%</td><td>ISO 527</td>

<td>Secant module, MD</td><td>23.2 priests</td><td>0.160 GPa</td><td>ISO 5527</td>

<td>Secant module, TD</td><td>24.7 priests</td><td>0.170 GPa</td><td>ISO 5527</td>

<td>Impact measurement by method falling element</td><td>0.198 lb</td><td>90.0 g</td><td>ISO 7765-1</td>

<td>Tensile strength of the film at break, MD</td><td>5800 psi</td><td>40.0 MPa</td><td>ISO 527</td>

<td>Tensile strength of film at break, TD</td><td>4350 psi</td><td>30.0 MPa</td><td>ISO 527</td>

<td colspan="4">Thermal properties</td>

<td>Melting temperature</td><td>252 ° F</td><td>122 ° C</td><td>ISO 11357-3</td>

<td colspan="4">Optical properties</td>

<td>turbidity</td><td> 10,0%</td><td> 10,0%</td><td>ASTM D 1003</td>

[0036] Polyolefins suitable for use in accordance with the present disclosure (e.g. polypropylene, polyethylene) can be produced by any suitable method. For example, the polyolefin can be made using a Ziegler-Natta catalyst, a metallocene catalyst, or combinations thereof. Polyethylene, for example, can be made using a chromium based catalyst or other suitable catalysts.

[0037] According to an embodiment, the polyolefin is prepared using Ziegler-Natta catalysts, which are usually based on titanium and organometallic aluminum compounds, for example triethylaluminum (C2H5) 3Al. Ziegler-Natta catalysts and processes for making such catalysts are described in US Patent Nos. 4,298,718; 4,544,717 and 4,767,735, each of which is cited in its entirety as a literature reference.

[0038] According to another embodiment, the polyolefin may be prepared using a metallocene catalyst. Metallocene catalysts can generally be characterized as coordination compounds having one or more cyclopentadienyl (Cp) groups (which may be substituted or unsubstituted, each substitution being the same or different) coordinated with a transition metal through a π bond. Examples of metallocene catalysts and methods for making such catalysts are described in U.S. Patent Nos. 4,794,096 and 4,975,403, each of which is cited in its entirety as a literature reference. Examples of polyolefins made using metallocene catalysts are described in more detail in US Patent Nos. 5,158,920;

5,416,228; 5,789,502; 5,807,800; 5,968,864; 6,225,251; 6,777,366; 6,777,367; 6,579,962;

6,468,936; 6,579,962; and 6,432,860, each of which is cited in its entirety as a reference source.

[0039] The polyolefin may also be prepared using any other catalyst or catalyst system such as a combination of Ziegler-Natta and metallocene catalysts, for example as described in US Patent Nos. 7,056,991 and 6,653,254, each of which is cited in its entirety as literature source.

[0040] The polyolefin can be produced by placing one or more olefin monomers (e.g. ethylene, propylene) alone or with other monomers in a suitable reaction vessel in the presence of a catalyst (e.g. Ziegler-Natta, metallocene, etc.) and under appropriate reaction conditions polymerization. Any suitable instrumentation and processes may be used to polymerize the olefin to obtain a polymer. For example, such processes may include solution phase, gas phase, suspension phase, volume phase, high pressure processes or combinations thereof. Such processes are described in more detail in US Patent Nos. 5,525,678; 6,420,580; 6,380,328; 6,359,072; 6,346,586; 6,340,730; 6,339,134; 6,300,436; 6,274,684; 6,271,323; 6,248,845; 6,245,868; 6,245,705; 6,242,545; 6,211,105; 6,207,606; 6,180,735; and 6,147,173, which are fully cited in the present description as a literature source.

[0041] According to an embodiment, the polyolefin is produced by a gas phase polymerization process. One example of a gas phase polymerization process is a continuous cycle system in which a recycle gas stream (otherwise known as a recycle stream or fluidizing agent) is heated in the reactor with the heat of the polymerization reaction. The heat is removed from the circulating gas stream in another part of the cycle using a cooling system located outside the reactor. A circulating gas stream containing one or more monomers can be cyclized continuously through a fluidized bed in the presence of a catalyst under reaction conditions. The circulating gas stream is generally withdrawn from the fluidized bed and re-cyclized in the reactor. At the same time, the polymer product can be removed from the reactor and fresh monomer can be added to replace the polymerized monomer. The pressure in the gas phase reactor can be from 100 psig to 500 psig or from 200 psig to 400 psig or from 250 psig to 350 psig. The temperature of the reactor in the gas phase process can be different from 30 ° C to 120 ° C or from 60 ° C to 115 ° C or from 70 ° C to 110 ° C or from 70 ° C to 95 ° C, for example as described in U.S. Patent Nos. 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,456,471; 5,462,999; 5,616,661; 5,627,242; 5,665,818; 5,677,375; and 5,668,228, which are cited in its entirety as a literature reference.

[0042] According to an embodiment, the polyolefin is formed in the suspension phase polymerization process. Slurry phase processes generally involve the suspension of a solid, particulate polymer in a liquid polymerization medium, to which monomers and optionally hydrogen, together with the catalyst, are added. The suspension (which may contain diluents) can be sporadically or continuously removed from the reactor, in which the volatile components can be separated from the polymer and recycled to the reactor, optionally after distillation. The liquefied diluent used in the polymerization agent may include C3 to C7 alkanes (e.g., hexane or isobutene). The agent used is generally liquid under polymerization conditions and relatively inert. The volume phase process is similar to a slurry process. However, the process may be a volumetric process, a slurry process, or a volumetric slurry process.

[0043] According to an embodiment, the multi-component article comprises at least one component comprising polylactic acid. Any suitable polylactic acid can be used in accordance with the present disclosure. For example, polylactic acid may include poly-L-lactide (PLLA), poly-D-lactide (PDLA), poly-LD-lactide (PDLLA) or combinations thereof. Polylactic acid can be produced using any suitable method. For example, polylactic acid can be separated by dehydration by condensation of lactic acid, as described in US Patent No. 5,310,865, which is cited in its entirety as a literature reference. Alternatively, polylactic acid can be produced by synthesis of cyclic lactide (also known as cyclic dimer) from lactic acid, followed by ring-opening polymerization of the cyclic lactide. An example of such a process is described in US Patent No. 2,758,987, which is cited in its entirety as a literature reference.

[0044] Catalysts can be used in the production of polylactic acid. The catalysts can be any type of catalyst suitable for the process. Examples of such catalysts include, without limitation, tin compounds such as tin octylate, titanium compounds such as tetraisopropyl titanate, zirconium compounds such as zirconium isopropoxide, and antimony compounds such as antimony trioxide.

[0045] Additives such as those previously described may be incorporated into the polylactic acid composition. Additional processes for producing polylactic acid are described in US patents

Of United States of America No. 5,821,327; 5,770,682; 5,508,378; 5,470,944; and 4,797,468, which are cited in its entirety as a reference source.

[0046] According to an embodiment, polylactic acid suitable for use in accordance with the present disclosure may have a density of 1.238 g / cm3³ up to 1.265 g / cm³,

3 3 3 alternatively from 1.24 g / cm³ up to 1.26 g / cm³ and alternatively from 1,245 g / cm³ up to 1.255 g / cm³determined in accordance with ASTM D792; melting index (210 ° C, 2.16 kg) from 5 g / 10 min to 35 g / 10 min, alternatively from 10 g / 10 min to 30 g / 10 min and alternatively from 10 g / 10 min to 20 g / 10 min determined in accordance with ASTM D1238; crystal melting point from 150 ° C to 180 ° C, alternatively from 160 ° C to 175 ° C and alternatively from 160 ° C to 170 ° C determined according to ASTM

D3418; glass transition temperature from 45 ° C to 85 ° C, alternatively from 50 ° C to 80 ° C and alternatively from 55 ° C to 75 ° C determined according to ASTM D3417; yield stress stretching from 4,000 psi to 25,000 psi, alternatively from 5,000 psi to 20,000 psi and alternatively from 5,500 psi to 20,000 psi determined according to ASTM D638; elongation at tension from 1.5% to 10%, alternatively from 2% to 8% and alternatively from 3% to 7% determined in accordance with ASTM D638; flexural modulus from 250,000 psi to 600,000 psi, alternatively from 300,000 psi to 550,000 psi and alternatively from 400,000 psi to 500,000 psi determined according to ASTM D790; Impact strength Izoda from 0.1 foot-pound / inch to 0.8 foot-pound / inch, alternatively from 0.2 foot-pound / inch to 0.7 foot-pound / inch and alternatively from 0.4 foot-pound / inch to 0.6 foot-pound / inch determined according to ASTM D256.

[0047] An example of polylactic acid suitable for use in accordance with the present disclosure includes without limitation NatureWorks 3051D, which is commercially available from

Nature Works LLC. According to an embodiment, polylactic acid suitable for use in accordance with the present disclosure (e.g., NatureWorks 3051D) may generally have the physical properties shown in Table 8.

Table 8

<td>properties</td><td>Typical 3051D value</td><td>Test method</td>

<td colspan="3">physical</td>

<td>₃Density, g / cm</td><td> 1,25</td><td>ASTM D792</td>

<td>Melting index (210 ° C, 2.16kg), g / 10 min.</td><td> 10-25</td><td>ASTM D1238</td>

<td>Melting point of the crystal, ° C</td><td> 150 - 165</td><td>ASTM D3418</td>

<td>Glass transition temperature, ° C</td><td> 55-65</td><td>ASTM D3417</td>

<td colspan="3">mechanical</td>

<td>Stretching at the yield point, psi</td><td> 7000</td><td>ASTM D638</td>

<td>Tensile elongation,%</td><td> 2,5</td><td>ASTM D638</td>

<td>Flexural modulus, psi</td><td> 555,000</td><td>ASTM D790</td>

<td>Impact strength Izod, foot-pounds / inches</td><td> 0,3</td><td>ASTM D256</td>

[0048] According to an embodiment, polylactic acid is present in the component in an amount of from 1 wt. up to 99 wt. based on the total weight of the multi-component article, alternatively from 5 wt. up to 70% by weight, alternatively from 10 wt% to 50% by weight According to an embodiment, polylactic acid is present in the component in an amount of 1 wt. up to 99 wt. based on the total weight of the multi-component article, alternatively from 5 wt. up to 70% by weight, alternatively from 10% by weight up to 50 wt.

[0049] According to an embodiment, the multi-component articles comprise at least one component comprising a reactive modifier. As used herein, reactive modifying agents mean polymer additives that, when added to molten polyolefin and PLA (e.g., PP / PLA blend or PE / PLA blend) form compounds in situ that serve to stabilize the connection between polyolefin and PLA. Compounds formed in situ have the effect of compatibilizers and reactive modifiers are precursors of these compatibilizers.

[0050] According to an embodiment, the reactive modifying agent comprises epoxy functional polyolefin. Examples of polyolefins with epoxy functional groups suitable for use in the present disclosure include, without limitation, epoxy functional polypropylene such as glycidyl methacrylate grafted polypropylene (PP-g-GMA), epoxy functional polyethylene such as polyethylene glycidyl methacrylate copolymer (PE- coGMA) or combinations thereof. An example of an epoxy functional polyethylene suitable for use in the present disclosure includes LOTADER AX8840, which is PE-co-GMA containing 8% GMA commercially available from Arkema.

[0051] According to another embodiment, the reactive modifying agent comprises PP-g-GMA. PP-g-GMA can be produced by any suitable method such as, for example, grafting GMA onto polypropylene in the presence of an initiator such as peroxide. Examples of initiators suitable for use in accordance with the present disclosure include without limitation LUPERSOL 101 and

TRIGANOX 301, which are peroxides commercially available from Arkema. According to an embodiment, the initiator can be used in an amount of from 0.03% to 2% by weight. based on the total weight of biodegradable polymer compositions, alternatively from 0.2 wt. to 0.8% by weight, alternatively from 0.3% by weight up to 0.5% by weight

[0052] The GMA grafting reaction to PP can be carried out in a molten state inside an extruder such as, for example, a single or twin screw extruder. In the following, such a process is referred to as reactive extrusion. The raw material comprising PP, GMA and initiator (i.e. peroxide) can be placed in the extrusion reactor in succession along the extruder, alternatively the raw material (i.e. PP, GMA and initiator) can be pre-mixed outside and placed in the extruder.

[0053] According to an alternative embodiment, PP-g-GMA is produced by grafting GMA onto polypropylene in the presence of an initiator and a multifunctional acrylate comonomer. The multifunctional acrylate comonomer may include polyethylene glycol diacrylate, trimethylolpropane triacrylate (TMPTA) or combinations thereof.

[0054] The multi-functional acrylate comonomer may additionally be characterized by a high flash point. The flash point is the lowest temperature at which it can form a flammable mixture with air, determined in accordance with ASTM D93. The higher the flash point, the less flammable the substance, which is an advantageous feature in the case of reactive melt extrusion. According to an embodiment, the multi-functional acrylate comonomer may have a flash point of 50 ° C to 120 ° C, alternatively 70 ° C to 100 ° C, alternatively 80 ° C to 100 ° C. Examples of multifunctional acrylate comonomers suitable for use in accordance with the present disclosure include without limitation SR259 (polyethylene glycol diacrylate), CD560 (alkoxylated hexanediol diacrylate) and SR351 (TMPTA), which are commercially available from Sartomer.

[0055] The reaction of the GMA grafting to polypropylene in the presence of peroxide and a multifunctional polyethylene glycol diacrylate acrylate comonomer is shown in Scheme 1.

<img file="PL2297385T3_D0001.tif" />

[0056] Without wishing to be bound by theory, the tertiary carbon atoms of the polypropylene molecules can easily be detached in the presence of peroxide during reactive extrusion to form polypropylene macro radicals with unpaired electrons. Polypropylene macro radicals, which are generally unstable, tend to form free radicals at a stage called "β-decay." Β decay refers to a family of reactions in which bonds in the beta position relative to the radical are cleaved resulting in the formation of a double bond and a new radical. It is believed that the β decay reaction is mainly the cause of the formation of double internal bonds, and therefore the occurrence is associated with the content of allyl in the final polymer. Usually β-degradation is more preferable to vaccination (i.e. addition of GMA), this results in both lower GMA grafting and polypropylene with a lower average molecular weight. However, in reactions involving a multifunctional acrylate comonomer, the function of this multifunctional acrylate comonomer is to easily capture polypropylene micro radicals resulting in a more stable intermediate (i.e. polypropylene acrylate radicals). The relatively stable propylene-acrylate radicals tend to react more easily with GMA, which is a monomer of the type of acrylate monomers, which in turn promotes grafting reactions.

[0057] In addition, as shown in Scheme 1, numerous free radicals may be present on grafted propyleneacrylate molecules, which makes it easier to capture and initiate the GMA reaction. The reactivity of GMA to free acrylate radicals may be higher than to tertiary polypropylene macro radicals. Consequently, PP-g-GMA prepared using a reaction mixture including a multifunctional acrylate comonomer may exhibit a higher degree of grafting than PP-gGMA prepared using an otherwise similar composition in the absence of the multifunctional acrylate comonomer. PP-g-GMA produced using a multifunctional acrylate comonomer is referred to below as highly grafted GMA (HGGMA).

[0058] According to an embodiment, HGGMA, which is a reactive modifier, is prepared using a reaction mixture comprising polypropylene present in an amount of from 80 wt. up to 99.5% by weight, alternatively from 90% by weight up to 99 wt. and alternatively from 95 wt. up to 99% by weight; GMA present in an amount of 0.5 wt. up to 20% by weight, alternatively from 1.0% by weight up to 10 wt. and alternatively from 1.0 wt. up to 5.0 wt. multifunctional acrylate comonomer (e.g. SE259) present in an amount of 0.5 wt. up to 15% by weight, alternatively from 1.0% by weight up to 10 wt. and alternatively from 1.0 wt. up to 5.0 wt. and initiator (e.g. LUPERSOL 101) present in an amount of from 0.05 wt. up to 1.5% by weight, alternatively from 0.2% by weight up to 0.8 wt. and alternatively from 0.3 wt. up to 0.5% by weight GMA: multifunctional acrylate comonomer in HGGMA may range from 1: 5 to 10: 1, alternatively 1: 2 to 5: 1 and alternatively 1: 1 to 3: 1. [0059] The amount of grafted GMA on the polyolefin may vary depending on many factors such as the type of substances used and the processing conditions. One skilled in the art can vary these parameters with the benefits of the present disclosure to produce reactive modifying agents with a user-desired grafting efficiency.

[0060] Vaccination efficiency may be determined using any suitable method. For example, vaccination efficiency can be determined by Fourier transform infrared spectroscopy (FTIR). According to an embodiment, one method of determining vaccination efficiency involves obtaining FTIR spectra for polymer samples with a mixture of PP and GMA in which the amount of each component is known. You can create a calibration curve by plotting the signal intensity at one or more wavelengths as a function of component concentration. The FTIR spectra of the PP-g-GMA sample can then be determined and compared to a calibration curve to determine vaccination efficiency. This method is described in more detail in Angew. Makromol. Chem, 1995, V229 pages 1-13. According to an embodiment, HGGMA may have a vaccination yield of 0.2 wt. up to 15% by weight, alternatively from 0.5% by weight up to 10% by weight, alternatively from 1.0% by weight up to 5.0 wt.

[0061] According to an embodiment, the reactive modifying agent is present in the component in an amount of 0.5 wt. up to 15 wt. based on the total weight of the multi-component article, alternatively from 1.0 wt. up to 10% by weight, alternatively from 3.0% by weight up to 5.0 wt.

[0062] According to an embodiment, the at least one component of the multi-component article comprises a compatible PLA and polyolefin blend. The blend can be compatible by mixing the components: PLA, polyolefin and reactive modifier, all types described herein, by reactive extrusion.

[0063] According to an embodiment, PP, PE, PLA and / or mixtures thereof may also contain additives to impart desired physical properties, such as printability, increased gloss or reduced blocking tendency. Examples of additives include, without limitation, stabilizing agents, ultraviolet screening agents, oxidizing agents, antioxidants, antistatic agents, ultraviolet absorbing agents, flame retardants, processing oils, release agents, coloring agents, pigments / dyes, filling agents, and / or other appropriate additions. The above-mentioned additives can be used alone or in combination with the formation of various polymer preparations. For example, stabilizers or stabilizing agents may be used to increase the protection of the polymer resin against degradation due to exposure to excessive temperatures and / or ultraviolet radiation. These additives can be used in amounts effective to give the desired properties.

[0064] In an embodiment, the PLA component of a multi-component article made using the composition of the present disclosure may be colored. According to such embodiments, coloring agents such as dyes or pigments may be added to PLA. This issue is described in detail later in this description. Effective amounts of additives and processes for adding these additives to the polymer compositions can be determined by one skilled in the art using the present disclosure.

[0065] According to an embodiment, the multi-component article may comprise one component comprising PLA and a second component comprising polyolefin and a reactive modifying agent. According to another embodiment, the multi-component article comprises one component comprising a blend of PLA and a polyolefin and a second component comprising a polyolefin and a reactive modifier. According to an embodiment, the multi-component article may comprise at least one component comprising a polyolefin (e.g. PP or PE), at least one component comprising PLA and at least one component comprising a polyolefin (e.g. PP or PE) and a reactive modifying agent, all of the types previously described herein. In the present specification, the component comprising polyolefin and reactive modifying agent is referred to as PORM such as PP / PP-g-GMA, PE / PE-co-GMA, etc.

[0066] According to an embodiment, the multi-component article may comprise at least one component comprising PP, at least one component comprising PLA, and at least one component comprising PP / PP-g-GMA, all of the types previously described herein. According to another embodiment, the multi-component article may comprise at least one component comprising PE, at least one component comprising PLA, and at least one component comprising PE / PE-co-GMA, all of the types previously described herein.

[0067] Without wishing to be bound by theory, the reactive modifying agent can be used to chemically combine components including polyolefin and components including PLA and / or to adhere to these components.

[0068] According to an embodiment, the multi-component article is a multi-component fiber. The multi-component fiber may include at least one component comprising a polyolefin (e.g. PP, PE), at least one component comprising PLA, and at least one component comprising PORM, all of the types previously described herein. According to an embodiment, the multicomponent fiber is a bicomponent fiber having a first component comprising PLA and a second component comprising PORM (e.g. PP / PP-g-GMA, PE / PE-co-GMA).

[0069] The bicomponent fiber may be produced by any method suitable for producing such a fiber. For example, the bicomponent fiber may be made by coextruding at least one component comprising PLA and at least one component comprising PORM. According to an embodiment, the components of the bicomponent fiber are melted, filled into the spinneret and coextruder hole to form fibers. According to an embodiment, the components of the fibers when extruded adhere to each other in the absence of substances or treatment promoting adhesion.

[0070] The fibers formed in this way can be cooled, for example, in air in a quenching column and then passed through a spinning finishing device, oriented and collected. Harvested fibers can additionally be treated, for example, they can be drawn to produce drawn fibers. The filaments or drawn fibers can be shaped to obtain various end products.

[0071] According to an embodiment, the bicomponent fiber may be shaped to obtain various configurations, for example as shown in Figure 1. Referring to Figure 1, the bicomponent fiber may be configured to obtain a sheath-core 110 or side-by-side configuration 120. Sheath-core 110 configuration it comprises outer shell 110A outer layer and core 110B inner layer. The sheath-core configuration 110 may be concentric 112 in which the center of mass of the core 112B coincides with the center of mass of the shell 112A or eccentric 114 in which the center of mass of the core 112B differs from the center of mass 112A of the shell. Figure 1 also shows a sheath-core configuration in a side view 116. According to an embodiment, the bi-component fiber core layer comprises PLA, alternatively the bi-component fiber shell layer includes PLA.

[0072] Side by side configuration 120 may include PLA page 120A and PORM page 120B. Figure 1 also shows a side-by-side configuration in front view 122 and side view 124.

[0073] The bicomponent fiber may have a total linear mass density of all components from 1 to 20 den per base fiber (dpf), alternatively from 1 to 15 dpf, alternatively from 2 to 10 dpf. One skilled in the art can select the linear mass density of individual components (e.g., PLA, polyolefin or PORM) by means of the present disclosure to obtain one or more properties desired by the user (i.e. physical properties, mechanical properties, etc.). For example, the bicomponent fiber may be made in a core-coating configuration in which the coating layer comprises PLA and the core layer comprises PP / PP-g-GMA. According to this embodiment, the core layer may have a linear mass density of 50% to 95% relative to the total linear mass density of the two component fiber, alternatively 60% to 90%, alternatively 70% to 90%.

[0074] According to an embodiment, the multi-component article is a multi-layer film. The multilayer film may comprise at least one layer comprising PLA, at least one layer comprising polyolefin (e.g. PP, PE) and at least one layer comprising PORM. As used herein, the reactive modifying agent can also be used to chemically combine the polyolefin component and PLA component and to increase cohesion. According to an embodiment, a multilayer film of the type described herein may have an increased adhesive strength between polyolefin and PLA compared to a similar multilayer film without PORM. The adhesive strength between polyolefin and PLA can be determined by measuring the force required to detach the polyolefin from PLA, determined in accordance with ASTM D3330 / 3330M-00. According to an embodiment, a multilayer film of the type described herein may have a polyolefin peeling force and PLA equal to or greater than 0.01 pounds exerted per inch of width (lb f / 1 width), alternatively equal to or greater than 0.1 lb f / 1 width, alternatively equal or greater than 0.5 lb f / 1 width, alternatively equal or greater than 1 lb f / l width, alternatively equal or greater than 2 lb f / 1 width.

[0075] In addition, a PORM layer comprising a reactive modifying agent may interact as a binder or binding layer that serves to improve the interfacial bond between PP and PLA or PE and PLA, resulting in a multilayer film with improved bonding compared to an otherwise similar multilayer film without a reactive modifier. Without wishing to be limited to theory, the reactive modifier may migrate to the interphase area of ​​the mix (e.g. PP and PLA) and serve as a tie layer.

[0076] The polyolefin and reactive modifying agent can be contacted prior to coextrusion to form a PORM mixture. According to an embodiment, PORM is polypropylene and PPg-GMA, alternatively PORM is polyethylene and PE-co-GMA. According to an embodiment, PLA, polyolefin and PORM are coextruded through a slit or die with two or more holes arranged in such a way that the extruded sheets join together to form the extruded composite sheet (i.e. multilayer film), in which the layers of film adhere to each other. The extruded composite sheet may have one or more PLA layers, one or more polyolefin layers, and one or more PORM layers. According to an embodiment, PLA, polyolefin (e.g. PP, PE) and PORM layers adhere directly to each other in a multilayer film in the absence of a substance or treatment that promotes adhesion. Such substances and treatments have been described previously in this specification.

[0077] According to an embodiment, the multilayer film is oriented. Generally, the orientation of a polymer composition refers to a process whereby the directivity (orientation of molecules relative to each other) is superimposed on the polymer configurations in the film. This orientation is used to give the desired properties to films such as, for example, strength and opacity. The term "biaxial orientation" as used herein refers to a process in which the polymer composition is heated to a certain temperature or temperature above the glass transition temperature but below the melting point of the crystal. Immediately after heating, the substance can then be extruded to obtain a film and stretched both in the longitudinal direction (i.e. the machine direction) and in the crossbar or transverse direction (i.e. towards the fabric spreader).

[0078] According to an embodiment, the biodegradable polymer composition of the type described herein is heated in an extruder. The molten polymer can then leave the device through the die and the molten plate can be used to produce extruded film, cast film, biaxially oriented film or the like. According to an embodiment, the molten plate can exit the device through the die and can be taken onto the roller without additional stretching to form an extruded film. Alternatively, the molten plate may exit the device through the die and may be uniaxially stretched as it is taken onto the cooled roller on which it is cooled to form a cast film.

[0079] According to an embodiment, the molten plate leaves the device through the die and is moved on a first roller (e.g., cooled roller) that cures the polymer composition to obtain a multilayer film. Then, the multilayer film can be oriented by stretching it in the longitudinal direction and the transverse direction. Longitudinal orientation is generally performed by using two successively arranged rollers, a second (or fast roller) operating at a certain speed relative to the slower roller corresponding to the desired orientation speed. Longitudinal orientation can alternatively be carried out using a series of rollers with increasing speeds, sometimes with additional intermediate shafts to control temperature and other functions.

[0080] After longitudinal orientation, the multilayer film can be cooled, preheated and moved to the transverse orientation section. Transverse orientation may include, for example, a fabric dilator mechanism in which the multilayer film is subjected to lateral pressure. Annealing and / or post-treatment may follow this orientation. Alternatively, the multilayer film can be stretched in both directions at the same time.

[0081] Without wishing to be limited to theory, after cooling, the molecular system imposed by stretching preferably competes with crystallization, and the drawn polymer particles condense to form a crystal lattice with crystal domains aligned in the direction of the tensile force. Additional disclosure regarding the production of biaxial film can be found in US Patent No. 4,029,876 and US Patent No. 2,178,104, each of which is cited in its entirety as a literature reference. [0082] Figure 2 illustrates various forms of multilayer films. Referring to Figure 2, in the configurations shown, PLA layers are designated A, PORM layers are designated B, and polyolefin layers are designated C. The multilayer film can be configured, for example, in such a way that the PORM layer can be a bottom layer as shown in 210, a core layer as shown in 220 or a cover layer as shown in 230. According to other embodiments, PORM can serve as a tie layer in which PORM supports the adhesion between the layers in which it is placed. For example, PORM can serve as a tie layer in a 3-layer film 240 in which it can be placed between PLA A and a polyolefin layer C. According to another embodiment, PORM can serve as a tie layer in 5-layer film 250, in which PORM first can be placed between the first PLA A layer and the polyolefin C layer and secondly the PORM can be placed between the polyolefin C layer and the second PLA A layer.

[0083] The multilayer film may have a total thickness (sum of the thicknesses of all layers) from 0.5 to 150 mils, alternatively from 1 to 50 mils, alternatively from 2 to 20 mils. The thickness of individual layers (PLA, PORM or polyolefin) may be selected by one skilled in the art using the present disclosure to obtain the properties desired by the user (i.e. physical properties, mechanical properties, etc.). For example, the multilayer film with the configuration shown in Figure 2, 240 may have a polyolefin layer with a thickness of 3% to 45% relative to the total thickness of the multilayer film, alternatively between 5% and 20%, alternatively between 5% and 10%; PORM as a tie layer between 0.2% and 30%, alternatively between 1.0% and 15%, and alternatively between 5% and 10%; and a PLA layer between 1% and 50%, alternatively between 5% and 40%, and alternatively between 10% and 30%.

[0084] Multi-component articles according to the present disclosure can be converted to final products by any suitable method. According to an embodiment, this transformation is a process for forming plastics such as blow molding, extrusion, injection blow molding, injection stretch blow molding, thermoforming and the like. Examples of final products that are obtained by shaping a biodegradable polymer composition of the type described herein include food packaging, office supplies, plastic items, replacement articles, patio formwork, structural props, laminate flooring compositions, polymer foam substrates; decorative surfaces (i.e. crown moldings, etc.), weather-resistant exterior materials, point-of-sale markings and display boards, household goods and consumer products, building insulation, cosmetics packaging, external replacement materials, lids and containers (i.e. for delicatessen, fruit, sweets and cookies), accessories, kitchen utensils, electronic parts, car parts, closures, protective headgear, paintball balls for reuse, toys (e.g. LEGO blocks), musical instruments, golf club emblems, pipes, business equipment and telephone components, shower heads, door handles, battery holders, wheel covers, front dummies for vehicles, etc. [0085] According to an embodiment, the multi-component articles of the present disclosure are fibers (e.g., multi-component fibers, bicomponent fibers, etc.) for use on woven fibers such as textiles, which can be further processed to form textile materials, for example, by weaving, knitting , crocheting, tying, squeezing the fiber or combinations thereof. According to another embodiment, these fibers can be used to reinforce concentrate and woven fibers such as yarns and fabrics for use as binding fibers in multi-fiber fabrics. Such multi-fiber fabrics can be used to make carpets.

[0086] According to an embodiment, the multi-component article is a multi-layer film in which the layer comprising the reactive modifier agent can serve as a core layer, a binding layer, a cover layer or a combination thereof. Additional end products will be apparent to those skilled in the art with the benefits of this disclosure.

[0087] The multi-component articles disclosed herein may exhibit increased interphase adhesion between components (e.g., PLA and polyolefins) compared to otherwise similar products without a component comprising a reactive modifying agent. As used herein, the term interfacial adhesion refers to adhesion in which connections between components are maintained by intermolecular forces, chain entanglement, or both, which provide the distance between combinations of components.

[0088] The multi-component articles disclosed herein may exhibit improved elasticity compared to otherwise similar articles without the PLA component. In the present description, the term elasticity refers to the substance's ability to absorb energy after elastic deformation and give it away after releasing the load. PLA has a higher elasticity than PE or PP, so biodegradable polymer compositions of the type described herein may exhibit increased elasticity compared to an otherwise similar composition without PLA. For example, a carpet made of bicomponent fibers of the type described herein may resist matting or crumbling when a force is applied. As another example, a fabric made of bicomponent fibers of the type described herein may exhibit improved wrinkle resistance.

[0089] The multi-component articles disclosed herein may exhibit improved stiffness compared to an otherwise similar article without the PLA component. PLA is more rigid than PE or PP, so a multi-component product may exhibit increased stiffness compared to an otherwise similar product without the PLA component. As used herein, the term stiffness refers to the resistance of a substance to shape changes. For example, in a multilayer film made as described herein, the PLA component may be an outer layer (e.g., a cover layer) that exhibits increased resistance to surface abrasions such as scratches, dents, chips, etc.

[0090] The multi-component articles disclosed herein may exhibit improved dyeability compared to an otherwise similar article without the PLA component. Increased compatibility with dyes and / or coloring agents, which are also usually polar, due to the polar nature of PLA. For example, the bicomponent fiber may be configured to obtain a core-sheath system of the type previously described herein, wherein the sheath may comprise PLA. Alternatively, the multilayer film can be configured such that the outer layers include PLA. In any embodiment, PLA may have the ability to more easily absorb a colorant or dye than an otherwise similar product without the PLA component.

[0091] The multi-component articles disclosed herein may exhibit improved printability compared to an otherwise similar article without the PLA component. Without wishing to be limited to theory, improved printability and / or improved surface treatment for printing can be achieved due to the polar nature of PLA. According to an embodiment, co-extruded PLA polyolefin sheets and films as cover layers may have surface printability or surface treatment properties similar to those seen for clean PLA films and / or sheets.

[0092] The multi-component articles disclosed herein may show improved scratch resistance compared to an otherwise similar article without the PLA component.

PLA is characterized by much higher rigidity and better scratch resistance than polyolefins. For example, coextruded PLA polyolefin sheets and films as cover layers may have surface scratches similar to clean PLA films and sheets. [0093] The multi-component articles disclosed herein may exhibit improved impact resistance compared to an otherwise similar article without the PLA component. Without wishing to be limited to theory, polyolefin sheets and films are harder than PLA sheets and films. Thus, coextruded PLA polyolefin sheets and films may have increased impact resistance compared to similar films and sheets made of PLA homopolymer.

EXAMPLES [0094] With the disclosure generally described, examples are given below as specific forms of the disclosure and to demonstrate its practical application and its advantages. It is understood that the examples are given as illustrations and are not intended to limit the description or the claims when they are used in any way. Below, unless indicated otherwise, the amount of ingredients in the composition or formulation is expressed as a percentage, which is the weight percentage of the component relative to the total weight of the composition.

EXAMPLE 1 [0095] The degree of GMA grafting onto polypropylene during the production of the reactive modifying agent (ie PP-g-GMA) was tested. Samples were prepared using a base polypropylene resin, 3276 and GMA with a flash point of 85 ° C and a viscosity of 2.7 cps. Base resin, 3276, is a polypropylene homopolymer commercially available from Total Petrochemicals, while GMA was commercially available from Dow Chemicals. Multifunctional acrylate comonomers were SR259 polyethylene glycol diacrylate (200) with a viscosity of 25 cps and SR351 trimethylolpropane triacrylate esters (TMTPA) 106 cps; both commercially available from Sartomer. The initiator used was peroxide LUPERSOL 101 (L101). The formulations are presented in Table 3 as parts by weight per hundred parts of base resin (phr). [0096] Fluff 3276 resin was mixed with the multifunctional acrylate comonomer (ie GMA) and initiator in a 50 liter mixer in 30 lbs. Then, the mixed fluff resin was placed in a MICRO-27 twin screw extruder at a set speed of 100 rpm with the possibility of stripping volatiles under vacuum and a throughput of 10 pounds / hour. The zone profiles were 400 ° F - 400 ° F - 395 ° F - 390 ° F - 380 ° F - 375 ° F - 370 ° F 365 ° F - 360 ° C - 360 ° F - 360 ° F - 360 ° F. The experimental treatment parameters are summarized in Table 9.

Table 9

<td></td><td colspan="4">preparations</td><td colspan="4">Extrusion parameters</td><td colspan="2">products</td>

<td>A sample #</td><td>Resin basic -wowa</td><td>GMA (Phr)</td><td>Como (Phr)</td><td>L-101 (Phr)</td><td>Performance (Lb / hr).</td><td>Impression not (turnover on minute)</td><td>Moment rotary (%)</td><td>Temp. topn./ciśn the Coverage (F / psi)</td><td>MFR (G / 10 min.)</td><td>GMA (%)</td>

<td># 1 (PP)</td><td>3276 fluff</td><td> 0</td><td></td><td> 0,05</td><td> 10</td><td> 100</td><td> 33</td><td> 385,6/310</td><td> 15,6</td><td> 0</td>

<td># 2 (PPgGMA</td><td>3276 fluff</td><td> 3</td><td></td><td> 0,30</td><td> 10</td><td> 100</td><td> 32</td><td> 389,0/250</td><td> 25,5</td><td> ~0,2 %</td>

<td> -3)</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td># 3 (PPgGMA -6)</td><td>3276 fluff</td><td> 3</td><td>1 (SR2 59)</td><td> 0,30</td><td> 10</td><td> 100</td><td> 29</td><td> 386/200</td><td> 36,2</td><td> ~3,0 %</td>

<td># 4 (P P-gGMA -7)</td><td>3276 fluff</td><td> 1,7</td><td>1 (SR3 51)</td><td> 0,30</td><td> 10</td><td> 100</td><td></td><td> -/-</td><td> 25,6</td><td> ~2,0 %</td>

[0097] Vaccination efficiency was then measured based on Fourier transform infrared spectroscopy (FTIR) spectra of the obtained PP-g-GMA products. PP-gGMA products were dissolved in hot xylene and precipitated with excess acetone. GMA oligomers are soluble in acetone. Precipitated PP-g-GMA was then dried in vacuo and pressed with KBr to give disks for FTIR analysis. Figure 1 shows the FTIR spectra of various samples

PP-g-GMA. Referring to Figure 1, the presence of polypropylene can be detected by the appearance of a vertex at 2722 cm^-1 in all samples. Sample 1 contains the substance after re-extruding the base resin with 0.05 phr peroxide. Sample 2 being GMA-grafted PP, prepared using conventional reactive extrusion formulations (i.e. in the absence of the multifunctional acrylate comonomer), showed negligible peak intensity of C = O at 1730 cm^-1, the tip being attributed to the GMA vaccine, which indicated that minimal GMA vaccination efficiency was achieved. However, in the presence of a multifunctional acrylate comonomer (Samples 3 and 4), a strong C = O apex was observed.

[0098] Closer examination of the tip of C = O at 1730 cm^-1 for Samples 3 and 4, shown in Figure 2, suggests that the signal is actually two overlapping vertices indicating that both

GMA as well as the multifunctional acrylate comonomer were grafted onto the polypropylene backbone.

Weak epoxy tip at about 860 cm^-1, which has been attributed to GMA molecules grafted onto the main polypropylene chains, is also visible in FTIR spectra. [0099] The graft yield (GMA%) was then calculated based on the FTIR results and is also shown in Table 9. With GMA as a pure monomer (without the multifunctional acrylate comonomer), the graft yield observed for Sample 2 was negligible. However, at a ratio of 3: 1 GMA: multifunctional acrylate comonomer, grafting efficiency increased as shown in Samples 3 and 4. PP-g-GMA prepared according to this example can be combined with other ingredients as described herein (e.g. PP and PLA ) to form biodegradable polymer compositions. Without wishing to be limited to theory, high PP-g-GMA vaccination may be more effective at compatibilizing polyolefin and PLA in biodegradable polymer compositions.

EXAMPLE 2 [0100] The peel strength of multilayer films (e.g., bilayer films) including polyolefin, reactive modifier and degraded polymer was tested. Four samples of two-layer films, designated as Samples 5-8, were obtained to obtain a 2 mil film with a 1.5 mil PP layer and a 0.5 mil PLA layer. Sample 5, which was a control, was made from PP3371 (3371), which is a commercially available polypropylene homopolymer from Total Petrochemicals USA, Inc. and coextruded with PLA 6201D (PLA) which is commercially available polylactic acid from Nature Works LLC. Sample 6 was prepared from a blend of 3371 with 3% PP-g-GMA (in which PP-g-GMA contains 2.5% GMA) and co-extruded with PLA. Sample 7 was prepared from a blend of 3371 with 3% LOTADER AX8900 (reactive modifier commercially available from Arkema) and coextruded with PLA. Sample 7, which was a comparative sample, was made from a blend of 3371 with 3% POLYBOND 3200 which is a cavitation enhancer containing 2.7% maleic anhydride commercially available from Chemtura and coextruded with PLA. Samples 5-8 were found to be clear and transparent after extrusion. Next, the peel force of each sample was determined in accordance with ASTM D3330 / 3330 M-00. The components of each sample and peel force test results are summarized in Table 10.

Table 10

<td rowspan="2">A sample</td><td colspan="2">Coextruded film (2 mils)</td><td rowspan="2">Peel force (lb f / 1 width)</td>

<td>PP (1.5 mils)</td><td>PLA (0.5 mils)</td>

<td> 5</td><td> 3371</td><td>PLA 6201D</td><td> 0</td>

<td> 6</td><td>3371 + 3% PP-g-GMA</td><td>PLA 6201D</td><td> 0</td>

<td> 7</td><td>3371 + 3% LOTADER</td><td>PLA 6201D</td><td> 0</td>

<td> 8</td><td>3371 + 3% POLYBOND</td><td>PLA 6201D</td><td> 0</td>

[0101] The results show that for all formulations tested, the films obtained were easy to peel off, indicating that the adhesion between the film layers was poor. Without wishing to be limited to theory, for films made from samples comprising only 3% of the reactive modifier (e.g. LOTADER AX8900 or PP-g-GMA), the concentration of the reactive modifier in the joints between PP and PLA layers may be insufficient. For films made from samples including such a reactive modifier, the reactive modifier present in the mass of PP may have had insufficient time to migrate to the connection between PP and PLA. PP and PLA in the absence of a reactive modifier could be characterized by the lack of sufficient chemical bonding during coextrusion, resulting in poor film adhesion.

EXAMPLE 3 [0102] The peel strength of multilayer films including polyolefin, reactive modifying agent and degradable polymer was tested. A control sample, designated Sample 9, was prepared from 3371, which was coextruded with PLA to give a 2-mil thick film containing 1.2 mil PP and 0.5 mil PLA.

[0103] Three samples, designated Samples 10-12, were prepared using a 1.2 mil thick PP layer, a 0.3 mil thick bond layer and a 0.5 mil thick PLA layer. Sample 10 was prepared from 3371 coextruded with PLA and a PP-g-GMA binding layer. Sample 11 was prepared from 3371 coextruded with PLA and a binding layer of LOTADER AX8900. Sample 12, which was a comparative sample, was prepared with 3371 coextruded with PLA and a binding layer of POLYBOND 3200. Then, the peel force of each sample was determined as described in Example 2. The components of each sample and peel force test results are summarized in Table 11.

Table 11

<td>A sample</td><td colspan="4">Coextruded film (2 mils)</td><td>Peel force (lbf / cal</td>

<td></td><td>PP (1.2</td><td>Binding layer (0.3</td><td>PLA</td><td> (0,5</td><td>width)</td>

<td></td><td>mil)</td><td>mil)</td><td>mil)</td><td></td>

<td> 9</td><td> 3371</td><td>not applicable</td><td>PLA 6201D</td><td> 0</td>

<td> 10</td><td> 3371</td><td>PP-g-GMA</td><td>PLA 6201D</td><td> ~0,3</td>

<td> 11</td><td> 3371</td><td>LOTADER</td><td>PLA 6201D</td><td>Too strong for the peel test</td>

<td> 12</td><td> 3371</td><td>POLYBOND</td><td>PLA 6201D</td><td> 0</td>

[0104] The results show that the film without any tie layer (Sample 9) and the film with POLYBOND as tie layer (Sample 12) were easily peeled off. Sample 10 with the PP-g-GMA binding layer showed increased adhesion between the layers with a peel force of about 0.3 lbf per inch width. Sample 11 with the LOTADER binding layer could not be peeled off, indicating that LOTADER increased the adhesion between PP and PLA. Not wanting to be limited to theory, LOTADER which contains more functional groups (e.g. epoxy groups) than PP-g-GMA can react more with PLA. Increased reactivity of LOTADER would result in an increased degree of chemical bonding between PLA and PP and increased interlayer adhesion as observed for Sample 11

EXAMPLE 4 [0105] The peel force of multilayer films of the type described herein was tested. A control sample, referred to as Sample 13, was prepared from 3371, which was co-extruded with PLA to form a 16 mil film with 14 mil PP and a 1.5 mil PLA film.

[0106] Three samples were produced, referred to as Samples 14-16, each of which had a 14 mil thick PP layer, a 0.5 mil thick tie layer and a 1.5 mil thick PLA layer. Sample 14 was prepared from 3371 coextruded with PLA and a PP-g-GMA binding layer. Sample 15 was prepared from 337 coextruded with PLA and LOTADER AX8900 binding layer. Sample 16, which was a comparative sample, was prepared with 3371 coextruded with PLA and a POLYBOND 3200 binding layer. Then, the peel force was determined for each sample as described in Example 2. The components of each sample and peel force test results are summarized in Table 12.

Table 12

<td rowspan="2">A sample</td><td colspan="4">Coextruded film (16 mils)</td><td rowspan="2">Peel force (lbf / cal width)</td>

<td>PP mils)</td><td> (14</td><td>Binding layer (0.5 mil)</td><td>PLA (1.5 miles)</td>

<td> 13</td><td colspan="2"> 3371</td><td>on</td><td>PLA 6201D</td><td> 0</td>

<td> 14</td><td colspan="2"> 3371</td><td>PP-g-GMA</td><td>PLA 6201 D</td><td> 0,2</td>

<td> 15</td><td colspan="2"> 3371</td><td>LOTADER</td><td>PLA 6201 D</td><td> 2,1</td>

<td> 16</td><td colspan="2"> 3371</td><td>POLYBOND</td><td>PLA 6201D</td><td> 0</td>

[0107] The results showed that the film without any tie layer (Sample 13) and the film with

POLYBOND as the binding layer (Sample 16) had a peel force of 0 and was easily peeled off, similar results as for Samples 9 and 12 of Example 3. Sample 14 having a PP-g-GMA binding layer showed increased adhesion with a peel force of 0, 2 lbf per inch wide. Sample 16 with LOTADER binding layer showed even greater adhesion with a peel force of 2.1 lb f per inch width.

[0108] The effect of film orientation on layer adhesion was investigated. The films were biaxially oriented at a 4x4 stretch ratio at 30 m / min stretch speed. Again, films made using Samples 13 and 16 were easily peeled off. Sample 14 was thin and detachable. Sample 15 resulted in a single clear layer after biaxial orientation and could not be torn off even when the film was significantly thinned.

[0109] Notwithstanding that certain embodiments have been shown and described, one of ordinary skill in the art can modify them without departing from the spirit and information contained in the disclosure. The specific forms described herein are exemplary only and are not intended to be limiting. Many variations and modifications of the forms disclosed herein are possible and are within the scope of the invention. In places where numerical ranges or limits are clearly indicated, it should be understood that such expressed ranges or limits including multiplied ranges or limits of similar sizes fall within clearly indicated ranges or limits (e.g., from about 1 to about 10 covers, 2, 3, 4, etc .; greater than 0.10 includes 0.11; 0.12; 0.13; etc.). For example, wherever a numerical range with a lower limit, RL, and an upper limit, RU, is disclosed, any number within the range is deemed to be specifically disclosed. In particular, the following numbers falling within a certain range are specifically disclosed: R = RL + k * (RU-RL), in which k is a variable from 1 percent to 100 percent with a 1 percent increase, i.e. k means 1 percent, 2 percent, 3 percent, 4 percent, 5 percent, ... 50 percent, 51 percent, 52 percent, ....., 95 percent, 96 percent, 97 percent, percent, 99 percent or 100 percent. In addition, any numerical range defined by two R numbers as defined above is also specifically disclosed. The intention to use the term "optionally" when referring to any item in the claim is to indicate that the item is required or, alternatively, not required. Both alternative indications fall within the scope of the claim. It is understood that the use of broader terms such as includes, fits, has, etc. supports narrower terms such as composition, essentially consists of, consisting essentially of, etc.

[0110] Accordingly, the scope of protection is not limited by the above description, but is only limited by the following claims, this scope includes all equivalents of the subject matter of the claims. Individual and each claims are included in the description as an embodiment of the present invention. Thus, the claims are an additional description and are an addition to the forms according to the present disclosure. The relevant comments do not constitute an admission that the above constitutes state of the art for the present invention, in particular any mention which may have occurred as a result of publication on the date following the priority date of this application. The disclosures regarding all patents, patent applications and publications cited herein are cited as literature sources to the extent that they provide ancillary details regarding the examples, procedure or other matters described herein.

Fina Technology, Inc. Proxy:

PL-PAT-2012-71

EP 2 297 385 B1