Thick blown films.

(54) Title: THICK BLOWN FILMS.

(54) Title: THICK BLOWN FILMS.

(57) Summary

The present invention is a film having a thickness greater than 100 microns comprising from 10 to 100% by weight of a polyethylene polymer made through the process of a) selecting a target polyethylene resin having a density, as shown determined according to ASTM D792, within the range of 0.90 glcm3 to 0.955 g / cm3, and a melt index, as determined according to ASTM D1238 (2.16 kg, 190C), within the range of 0.01 g / 10 minutes at 10 g / 10 minutes; b) reacting the target polyethylene with an alkoxyamine derivative in an amount less than 900 parts of derivative per million parts by weight of the total polyethylene resin under conditions sufficient to increase the melt strength of the target polyethylene resin; and c) forming a thick film from the modified target resin. Films of the present invention include those that can achieve similar processability to those containing unmodified linear polyethylene despite having at least 10% fewer LDPE reams in the formulation.

(57) Abstract

The present in vention ¡sa film having a thickness greater than 100 microns comprising from 10 to 100 percent by weight of a polyethylene polymer made by the process of a) selecting a target polyethylene resin having a density, as determined according to ASTM D792, in the range of from 0.90 g / cm3 to 0.955 g / cm3, and a melt Index, as determined according to ASTM D1238 (2.16 kg, 190C), in the range of from 0.01 g / 10min to 10 g / 10 min; b) reacting said target polyethylene with an alkoxy amine derivative in an amount less than 900 parts derivative per million parts by weight of total polyethylene resin under conditions sufficient to increase the melt strength of the target polyethylene resin; and c) forming a thick film from the modified target resin. The present films include those which can achieve similar processability as those containing unmodified linear polyethylene despite having at least 10% less LDPE resins in the formulation.

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PATENT TITLE NO. 347015

Mexican Institute of Property

Industrial □

Owner (s): DOW GLOBAL TECHNOLOGIES LLC .; DOW BRASIL SA

Address: ²⁰⁴⁰ DowCenter, Midland, Michigan, 48674, USA

Denomination: THICK BLOWN FILMS.

Classification: lnt.CI.8: C08F10 / 02; C08F210 / 16; C08F8 / 00; C08F8 / 30; C08J3 / 22; C08J5 / 18; C08K5 / 32; C08K5 / 3435; C08L23 / 04; C08L23 / 06; C08L23 / 08; C08L23 / 36

Inventor (s): NICOLAS MAZZOLA; JORGE GOMES; MARIA POLLARD; MiCHAEL TURNER

REQUEST

Numbers International filing date:

MX / a / 2012/008101 January 11, 2011

PRIORITY

Country: Date: Number:

US January 11, 2010 12 / 685,148

Validity: Twenty years

Expiration Date: January 11, 2031

The reference patent is granted based on articles 1, 2, section V, 6, section III, and 59 of the Industrial Property Law.

In accordance with article 23 of the Industrial Property Law, this patent is valid for twenty years, non-extendable, counted from the date of filing of the international application and will be subject to the payment of the fee to keep the rights in force. _;

Whoever signs this title does so based on the provisions of articles 8 ° sections lll and 7 ° bis 2 of the Industrial Property Law (Official Gazette of the Federation (O OF.) 08/27/1991, amended on 08/02/1994, 10/25/1996, 12/26/1997, 05/17/1999, 01/26/2004, 06/16/2005, 01/25/2005, 05/06/2009, 06 / 01/2010, 06/18/2010, 08/28/2010, 01/27/2012 and 04/09/2012); Articles 1, 3^or fraction V part a), 4^or and 12th sections I and III of the Regulations of the Mexican Institute of Industrial Property (DOF 12/14/1999, amended on 07/01/2002, 07/07/2004, 07/28/2004 and 09/07/2007) ; items 1^or, 3°, 4°, 5^or Section V subsection a), 16 sections I and III and 30 of the Organic Statute of the Mexican Institute of Industrial Property (DOF 12/27/1999, amended et 10/10/2002, 07/29/2004, 08/04/2004 and 09/13/2007); 1^or, 3^orand 5^or subsection a) of the Agreement that delegates powers to the Deputy General Directors, Coordinator, Divisional Directors, Heads of Regional Offices. Divisional Deputy Directors, Departmental Coordinators and other subordinates of the Mexican Institute of Industrial Property. (DOF 12/15/1999, amended on 02/04/2000, 07/29/2004, 08/04/2004 and 09/13/2007).

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MX / 2017/30651

THICK BLOWN FILMS

IMPI ifeRTmzro Mexican

OF THE INDUSTRIAL FROHEDAD

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Cross Reference with Related Requests

The present application claims priority to US Patent Application Serial No. 12 / 685,148, filed January 11, 2010, the disclosure of which is incorporated herein by reference, for purposes of United States practice.

Background of the Invention

Polyethylene has desirable properties that have helped it to be the highest volume manufactured polymer. Polyethylene can be made from different processes, in order to provide different properties. Known families of polyethylene include high density polyethylene (HDPE), linear low density polyethylene (LLDPE), and low density polyethylene made using high pressure reactors (LDPE). Within these broad classes, there are many variations that result from different types of polyolefin process technologies (e.g. solution, paste, or gas phase) or from the use of different catalysts (e.g. Ziegler-Natta or restricted geometry catalysts ). The desired application requires a careful balance of theological properties which will lead one skilled in the art to select one type of polyethylene relative to another. In many applications, such as n

IMPI

INSTITUTO MUICANl ... . . . . . ... blow molding or blown film applications,

<img file="MX347015B_D0004.tif" />

melt resistance of polyethylene is a key factor, often measured as polymer elongation viscosity.

Melt strength is a practical measure that can anticipate material performance when subjected to elongation strains. In melt processing, good elongation viscosity is important to maintain stability during processes such as coating, blown film production, fiber spinning, and foamed parts.

Melt resistance directly effects various processing parameters such as bubble stability, and therefore thickness variation during blown film production; the formation of parison during the blow molding process; skewing during profile extrusion; the formation of cells during the foam generation process; a more stable thickness distribution during sheet / film thermoforming.

This property can be improved by using higher molecular weight resins, although such resins will generally require more robust equipment and more energy use because they tend to generate higher extrusion pressure during the extrusion process. Therefore, the properties must be balanced to provide an acceptable combination.

<img file="MX347015B_D0005.tif" />

<img file="MX347015B_D0006.tif" />

IMPI • Wi / Vuto ir i ° EI * nomOAD of physical properties and processing capacity.^{,To the}

In thick film applications? Te utrH ^ an— combinations of LDPE and LLDPE in order to obtain a balance in the processing capacity (amps and extruder pressure) and mechanical properties of the film. In this combination, the LDPE component is the throughput component, while the LLDPE is the mechanical end component. Accordingly, the ability to decrease the LDPE portion of the blend must increase the mechanical properties of the blend. Through the present invention, the ability to increase the melt strength of the LLDPE component allows the use of a higher percentage of the LLDPE blend, thereby increasing mechanical properties without sacrificing processability.

Brief Description of the Invention

Accordingly, one aspect of the present invention is a film particularly suitable for thick film applications. For the purposes of the present invention, a "thick film" is one that has an average thickness of at least 100 microns, and for many applications one that has an average thickness greater than 200 microns. The films of the present invention comprise a polyethylene that has been reacted with an alkoxyamine derivative through an extrusion-guided process.

IMPI

INMHUIU MEXICANO D »LA MOHEDAL 'INDUSTRIAL

Accordingly, one aspect of the present invention is

<img file="MX347015B_D0007.tif" />

a film having a thickness greater than 200 microns, comprising a polyethylene polymer made through a process of first selecting a target polyethylene resin having a density, as determined in accordance with ASTM D792, within the range of 0.90 g / cm³ at 0.955 g / cm³, and a melt index, as determined according to ASTM D1238 (2.16 kg, 190 ° C), within the range of 0.01 g / 10 min to 10 g / 10 min. Subsequently, the target polyethylene is reacted with an alkoxyamine derivative in an amount less than 900 parts of derivative, per million parts by weight of the total polyethylene resin under conditions sufficient to increase the melt strength of the target polyethylene resin. . This subsequently modified target resin is combined with a quantity of low density polyethylene prepared in a high pressure process, and the combined resin is subsequently used to make a film.

Modified target resins for use in the present invention increase elongation viscosity in low-level shear ranges (0.1 s ¹), while maintaining viscosity in higher shear ranges (&gt; 100 s ~¹) so that the ease of processing of the material is maintained under typical extrusion conditions. One aspect of the present invention is that the extruder pressure does not

IMPI ^ ii »imriuMiucM« or increases more than 10% of the resin comparatitf ^ iHíís? ^ Of the processing of the resin of the prpgpntp invpnrión under the same operating conditions.

Brief Description of Figures

Figure 1 shows the curve of resistance to melting versus stretching speed with increasing additive concentration.

Figure 2 shows the viscosity versus the frequency of the cut-off range measured using a constant temperature of 190 ° in a frequency sweep in a TA Instruments “Advanced Rheometric Expansion System (ARES)” .

Figure 3 shows the melt resistance of the combinations of the present invention and the comparative resin versus the amount of LDPE F resin.

Detailed description of the invention

In its broadest sense, the present invention is a film having a thickness greater than 200 microns, comprising:

a) 10 to 100 percent by weight of the polyethylene polymer made by the process of:

i) selecting a target polyethylene resin that has a density, as determined in accordance with ASTM D792, within the range of 0.90 g / cm³ at 0.955 g / cm³, and a melt index, as determined in accordance with ASTM 'w and

<img file="MX347015B_D0008.tif" />

IMPI trtsrnvro MEXICAN

D1238 (2.16 kg, 190 ° C), within the range of 0.01 g / 10 min; __ i) reacting the target polyethylene with an alkoxyamine derivative in an amount less than 900 parts of derivative per one million parts by weight of the total polyethylene resin under conditions sufficient to increase the melt strength of the polyethylene resin target; Y

b) from 0 to 90% by weight of a low-density polyethylene composition.

Polyethylene resin includes all polymers and polymer blends that are derived from at least 50% by weight of the ethylene monomer units. This includes materials known in the art such as high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE) (including Ziegler-Natta linear low-density polyethylene (LLDPE), metallocene polyethylene, and multi-reactor polyethylene (combinations "in Ziegler-Natta PE PE and metallocene PE "reactor, such as the product described in US Pat. Nos. 6,545,088 (Kolthammer, et al.); 6,538,070 (Cardwell, et al.); 6,566,446 (Parikh, et al.); 5,844,045 (Kolthammer, et al.); 5,869,575 (Kolthammer, et al.); and 6,448,341 (Kolthammer, et al.)), and low density polyethylene using high pressure reactors (LDPE).

The selected target polyethylene resin must have

IMPI ^ a density, as determined from acü®ffó &amp;_F^ g ^ g

D792, within the range of 0.865 g / cm³ at 0.962 g / cm³, more preferably 0.905 g / cm3 to 0.957 g / cm³ at a melt index, as determined according to ASTM D1238 (2.16 kg, 190 ° C), within the range of 0.01 g / 10 min to 100 g / 10 min, more preferably 0.1 g / 10 min to 15 g /10 minutes. Suitable target polyethylene resins can be produced with conventional Ziegler Natta or Chromium catalysts, but also metallocene or single site catalysts. Such resins can have monomodal or multimodal molecular weight distributions.

Once the target polyethylene resin is selected, it is reacted with an alkoxyamine derivative. For the purposes of the present invention, "alkoxyamine derivatives" include nitroxide derivatives. The alkoxyamine derivative is added in an amount and under conditions sufficient to increase the melt strength of the polyethylene resin. The alkoxyamine derivatives correspond to the formula:

(R₁) (R₂) NOR₃ where Ri and R₂ each are independently of each other, hydrogen, C₄-C₄₂ alkyl or C₄-C₄₂ aryl or substituted hydrocarbon groups comprising O and / or N, and wherein Ri and R₂ they can form a ring structure together; and where R₃ is hydrogen, a hydrocarbon or a group of

IMPIAS

INSTITUTO MEXICANO DE LA PEOPIBDAO substituted hydrocarbon comprising O and / or N. Te ^^ rupbK preferred for R₃ include -CT-Cigalkyl; -Oa-Gibai ilu, -C'F C₁₉alkenyl; -OC.-C ^ alkyl; -OC₆-C₁₀aryl; -NH-C ^ Ci₉I rent; -ΝΗ-Ο₆-Ο₁₀3πΙο; -N- (Ci-C₁₉rent)₂, R₃ more preferably contains an acyl group.

The preferred compound can form a nitroxyl radical (R1) (R2) NO * or aminyl radical (R1) (R2) N * after decomposition or thermolysis.

A particularly preferred species of the alkoxyamine derivative is 9- (acetyloxy) -3,8,10-triethyl7,8,10-trimethyl-1,5-dioxa-9-azaspiro [5.5] undec-3-yl octadecanoate ] methyl which has the following chemical structure:

<img file="MX347015B_D0009.tif" />

I

Examples of some preferred species for use in the present invention include the following:

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<img file="MX347015B_D0011.tif" />

<img file="MX347015B_D0012.tif" />

<img file="MX347015B_D0013.tif" />

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<img file="MX347015B_D0016.tif" />

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INSTITUTO MEXICANO • E LA FHOPltDAD INDUSTUIAL

<img file="MX347015B_D0017.tif" />

<img file="MX347015B_D0018.tif" />

In general, hydroxylamine esters are more preferred with a particularly preferred hydroxylamine ester being 9- (acetyloxy) -3,8,10-triethyl octadecanoate.

7,8,1 0-trimethyl-1,5-dioxa-9-azaspiro [5.5] undec-3-yl] methylW^ST’^IAL

IMPI

INSTITUTO MEXICANO M LA ntOHCDAD

<img file="MX347015B_D0019.tif" />

Alkoxyamine derivatives are added in sufficient quantity to increase the melt strength and / or increase the elongation viscosity to the desired level. Preferably, the melt strength is increased by at least 10%, 20%, 25%, 35% or even 50% compared to a similar resin, which has not been reacted with an alkoxyamine derivative. In general, the alkoxyamine derivatives are added in an amount of 1 to 900 ppm of the total amount of the polyethylene polymer by weight (this is 1 to 900 parts of alkoxyamine derivative per one million parts of the target resin plus the resin carrier, if one exists). Preferably 15 to 600 ppm, more preferably 25 to 400 ppm and even more preferably 30 to 200 ppm.

The addition of the polyethylene polymer can be carried out in all customary mixing machines, in which the polymer is melted and mixed with the additives. Suitable machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders.

The process is preferably carried out in an extruder, introducing the additive during processing. Particularly preferred processing machines are single screw extruders, counter rotating and joint rotating twin screw extruders, gear extruders

<img file="MX347015B_D0020.tif" />

planetary, ring extruders and kneaders suitable in Handbuch der Kunststoftextrusion Publications, Vol. 1 Grundlagen, Editors F. Hensen, W. Knappe, H. Potente, 1989, pp. 3-7, ISBN 3-446-14339-4 (VoL 2 Extrusionsanlagen 1986, ISBN 3-446-14329-7). For example, the length of the screw can be 1 to 60 times the diameter of the screw, preferably 35 to 48 times the diameters of the screw. The speed of rotation of the screw is preferably 10 to 600 rotations per minute (rpm), more preferably 25 to 300 rpm. It is also possible to first prepare a concentrated mixture of the additive in a polyethylene resin carried, preferably from 1000 to 10000 ppm, and later introduce this concentrate, or "master batch" through an extruder into a molten polyethylene using a static mixer to combine the two materials, preferably in 1 to 20% by weight of the concentrate in the molten resin. The concentrate can be processed in an extruder, preferably at temperatures of 180 to 240 ° C. Temperatures in the static mixer can fluctuate from 200 to 250 ° C, with a residence time in the mixer fluctuating from 1 to 10 minutes.

The maximum performance depends on the diameter of the screw, the speed of rotation and the transmission force. The process of the present invention can also be carried out at a level lower than maximum performance, by varying the parameters

IMPI ^

MEXICAN INSTITUTE

DE LA MOHEDAL V&gt; - '' W.

mentioned or using weighing machines ^ '^ u ^ - ^³ provide dosage amounts. ..... .......— ——

If a plurality of components are added, they can be premixed or added individually.

Polymers need to be subjected to an elevated temperature for a sufficient period of time so that the desired changes occur. The temperature is generally above the softening point of the polymers. In a referred embodiment of the process of the present invention, a temperature range below 280 ° C, particularly from about 160 ° C to 280 ° C is employed. In a particularly preferred variant of the process, the temperature range of about 200 ° C to 260 ° C is used.

The period of time required for the reaction can vary as a function of a temperature, the amount of material to be reacted and the type, for example, of extruder used. Typically it is about 10 seconds to 30 minutes, in particular 20 seconds to 20 minutes.

The alkoxyamine derivative can be conveniently added to the mixing device by using a master batch. As will be appreciated by those skilled in the art, the master batch carrier resin can be chosen as compatible with the resin to be modified. Low-density polyethylene polymers of

IMPI ^

INSTITUTE MiXICANO

PROFIfTY OF high pressure LDPE (referred to in the industry as “LD'PP * 7&gt;¹ It is the preferred conveyor due to the lower 'Tedctivielad, laf as evidenced by the little variation in extrusion pressure during master batch production. HDPE can be a better carrier, as it will react even less, because it has no tertiary carbons and very low trisubstituted unsaturation units per 1,000,000 carbons.

Another advantage of the present invention is the discovery that polypropylene is not a good carrier for this additive, as it tends to degrade at typical processing temperatures. Another discovery is that the carrier resin must be substantially free of any antioxidant additives, preferably having less than 1,000 ppm of the antioxidant additives, as they tend to suppress the activity of the additive.

The preferred carrier resin should be compatible with the application at hand; it should have a viscosity similar to that of the target polyethylene resin, with which it will be blended. An LDPE or HDPE resin with minimal trisubstituted unsaturation units should be preferred, preferably less than 70 preferred carrier resin, (Mn) that is less than 50,000, process, as demonstrated by 1,000,000 carbons. The should have a molecular weight so that it is easy to through the pressure drop

INSTITUTO MEXICANO through the extruder. The carrier resin of other additives for processing aidsarrue_n ± a ^ __ aiLnq.Lie _____ should preferably be substantially free of antioxidant compounds, preferably containing less than 1,000 ppm of any antioxidant compound, preferably less than 500 ppm, more preferably less than 100 ppm in weight.

The target polyethylene resin can be a copolymer of ethylene with any alkene monomer containing 3 to 12 carbons. Preferably, the target polyethylene resin should have a trisubstituted unit unsaturation level per 1,000,000 carbons ranging from 200 to 450. It should have a slightly lower molecular weight than the carrier resin, as indicated by the melt index (g /10 minutes). Preferably, the melt index of the target polyethylene resin should be greater than 0.2 to 0.5 units (g / 10 min) than the final desired resin. Preferably, the polyethylene resin should contain minimal or no antioxidant additives, and any additives may be well dispersed in the resin prior to being combined with the carrier resin.

The amount of the alkoxyamine derivative material in the carrier resin should be within the range of 0.1 to 30% by weight, preferably 0.1 to 5%, and more preferably within the range of 0.2 to 1%. The quantity of the master batch is added so that the alkoxyamine derivative is a ^ r ^^ hüo to the target product within a range of 10-to-906-ppfTT preferably 15 to 600 ppm, more preferably 25 to

400 ppm and even more preferably 30 to 200 ppm. It will be readily understood by one of ordinary skill in the art, that the amount of alkoxyamine derivative in the final product will be reduced from the amounts added, as the compound reacts with the carrier and target polyethylene.

Preferably, the amount of the alkoxyamine derivative ingredient should be kept below 1000 ppm to minimize the reaction in the carrier resin, reduce the potential for gels in the final product, and substantially react in the final product, so that the final product remains. stable with additional processing. It should be understood that after the alkoxyamine derivative has been allowed to react with the target resin, it may be advisable to add one or more oxidizing additives, to protect the properties of the modified target resin. One way to achieve this is to combine the resin after reaction with the alkoxyamine derivative with another resin that is high in antioxidants.

The modified target polyethylene should comprise from 10 to about 100% by weight of the film. A second optional component of the film is a resin

IMPI

LDPE, which can comprise from 0 to 90% cfe '^ iSsSQ of the advantages of the present invention, is the ability to reduce the amount of LDPE, while maintaining the desired mechanical properties of the film, so that in modalities Preferably, the film comprises less than 25%, preferably less than 10% and even more preferably less than 5% by weight of LDPE.

Said low-density polyethylene composition can have a density within the range of 0.910 g / cm³ at 0.940 g / cm³; for example 0.915 g / cm³ at 0.935 g / cm³, and a melt index (l₂) within the range of 0.1 to 5 g / 10 minutes; for example, 0.2 to 2 g / 10 minutes. The target resin (which itself may be a blend that includes LDPE) can be conveniently reacted first with the alkoxyamine derivative and subsequently combined with the LDPE.

Applications

Ethylene polymer can be employed in a variety of conventional thermoplastic manufacturing processes to produce useful articles, including objects that comprise at least one layer of film, such as a monolayer film, or at least one layer in a multi-layer film. Prepared by casting, blowing, sintering or extrusion coating processes.

Additives and adjuvants can be added to the polymer

Ethylene IMPI, after formation. INtxKTwim additives include fillers such as organic or inorganic particles, including clays, talc, titanium dioxide, zeolites, powdered metals, organic or inorganic fibers include carbon fibers, silicone nitride fibers, steel wire or mesh, and nylon cord or polyester, nano-sized particles, clays, etc .; adhesives, oil extenders, including paraffinic or naphthalene oils; and other natural and synthetic polymers, including other polymers that are or can be made according to the methods of the embodiments.

The film can also comprise additional components, so that the film comprises blends or blends of the ethylenic polymers with other polyolefins. Suitable polymers for combining with the ethylenic polymers described above include thermoplastic and non-thermoplastic polymers including natural and synthetic polymers. Exemplary polymers for blending include various types of polyethylene, including high pressure, free radical low-density polyethylene (LDPE), Ziegler-Natta linear low-density polyethylene (LLDPE), metallocene PE, including multi-reactor PE ( "in-reactor" combinations of Ziegler-Natta PE and metallocene PE, such as the products described in US Patent Nos. 6,545,088 (Kolthammer, et al.);

<img file="MX347015B_D0021.tif" />

6,538,070 (Cardwell, et al.);

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B.seWTKSSSSa INDUSTRIAL

<img file="MX347015B_D0022.tif" />

associates); 5,844,045 (Kolthammer, et al.); 5,869,575 (Kolthammer, et al.); and 6,448,341 (Kolthammer, et al.)).

The ethylenic polymer can be used as a thick film resin. Surprisingly, the additive has been shown to improve the melt resistance of the resins of the present invention, while having better processability than resins with similar melt resistance, as indicated by the required energy. in an extruder in film material processing. When this ethylenic polymer is combined with LDPE resins, it exhibits a higher melt resistance than the equivalent combination that does not contain the additive.

TEST METHODS

Density

Samples that are measured in accordance with ASTM D 1928. Sample press times, for density, are prepared from measurements made in one using ASTM D792, Method

B.

melt index

The melt index, MI ol₂, is measured according to

ASTM D 1238, Conditions 190 ° C / 2.16 kg, and is reported in grams eluted per 10 minutes.

₁₀ it is measured

<img file="MX347015B_D0023.tif" />

industrial

ASTM D 1238, Conditions 190 ° C / 10 kg, and is reported in grams eluted per 10 minutes.

Melt Resistance

Melt strength is measured at a temperature of 190 ° C, using a Goettfert Rheotens 71.97 (Góettfert Inc .; Rock Hill, SC), food melt with a Góettfert Rheotester 2000 capillary rheometer equipped with a flat inlet angle (180 degrees) with a length of 30 mm and a diameter of 2 mm. Pellets are fed into the barrel (L = 300mm, Diameter = 12mm), compressed and allowed to melt for 10 minutes before being extruded at a constant piston speed of 0.265mm / s, which corresponds to the cutting range 38.2s' wall¹ in the determined die diameter. The extrudate passes through the wheels of the Rheotens located 100 mm below the die, exit and are extracted by the wheels that are below in an acceleration range of 2.4 mm / s². The force (in cN) exerted on the wheels is recorded as a function of the wheel speed (in mm / s). The melt strength is reported as the platen force (cN) before the strand breaks.

Dynamic Mechanical Spectroscopy

Elongation viscosity is measured using the Dynamic Mechanical Spectroscopy (DMS) method. Dynamic oscillatory shear measurements are carried out with

<img file="MX347015B_D0024.tif" />

TA Instruments (New Castle, DE) at a tempQiatiua-de-4-9e * © 7 using 25 mm parallel plates with a 2.0 mm gap and at a constant 10% strain under an inert nitrogen atmosphere. The frequency range is 0.1 to 100 radians / second at 5 points per decade logarithmically separated. The stress response is analyzed in terms of amplitude and phase, from which the storage modulus (G '), loss modulus (G "), complex modulus (G'), tangent δ, phase angle δ are calculated. and complex viscosity (η *). The amplitude of the strain is constant at 10%. The response to stress is analyzed in terms of amplitude and phase, from which the storage modulus (G '), loss modulus (G "), complex modulus (G *), dynamic viscosity (η *) are calculated. , and tangent (δ) or tangent delta. For sample preparation, the resins are compression molded into a 3mm thick x 25mm diameter circular plate at a temperature of 177^andC for 5 minutes under a pressure of 10 MPa in air, and subsequently cooled.

Gel Permeation Chromatography

The Triple Detector Gel Permeation Chromatography System (3D-GPC or TD-GPC) consists of a Waters (Milford, Mass) 150 ° C high temperature chromatograph (other suitable high temperature GPC instruments include Polymer Laboratories (Shropshire , UK) Model 210 and

Model 220 equipped with a d (Rl) refractometer. Additional detectors may include a * ^ * ^ infrared IR4 from Polymer ChAR (Valencia, Spain), Precision Detectors (Amherst, Mass.) Model 2040 2-angle laser light scatter detector (LS), and a viscometer from Viscotek (Houston, Tex.) 150R solution of 4 capillaries. A GPC with these last two independent detectors, and at least one of the forming detectors is sometimes referred to as "3D-GPC or TD-GPC", while the term "GPC" alone generally refers to conventional GPC. Depending on the sample, a 15 ° angle or a 90 ° angle is used for calculation purposes for the light scattering detector. Data collection is carried out using Viscotek TriSEC Version 3 software, and a 4-channel Viscotek Data Manager DM400. The system is also equipped with an in-line solvent gas extraction device from Polymer Laboratories (Shropshire, UK).

Suitable GPC high temperature columns can be used, such as 12 micron Shodex HT803 12 inch long columns or 4 12 inch Polymer columns with a mixed pore size packing of 20 micron Labs (MixA LS, Polymer Labs). The sample carousel compartment is operated at a temperature of 140 ° C and the column compartment is operated at a temperature of 150 ° C. The samples are prepared at a concentration of 0.1 grams of polymer in

INSTITUTO MEXICANO jH milliliters of solvent. The sample preparation solvent chromaf $$ C $$ £ § contains 200 ppm of butylated hydroxytoluene (BHT) in trichloro benzene (TCB). Both solvents are flushed with nitrogen. The polyethylene samples are gently shaken at 160 ° C for 4 hours. The injection volume is 200 microliters. The flow rate through the GPC is set to 1 ml / minute.

The GPC column assembly is calibrated, running 21 low molecular weight distribution polystyrene standards. The molecular weight (MW) of the standards ranges from 580 to 8,400,000, and the standards are contained in 6 "cocktail" mixes. Each standard mixture has at least a decade of separation between individual molecular weights. Standard mixes are purchased from Polymer Laboratories. Polystyrene standards are prepared in 0.025 g in 50 mL of solvent for molecular weights equal to or greater than 1,000,000 and 0.05 g in 50 mL of solvent for molecular weights less than 1,000,000. The polystyrene standards are dissolved at a temperature of 80 ° C with gentle agitation for 30 minutes. Narrow standard mixes are run first, and in order to decrease the amount of the higher molecular weight component to minimize degradation.

The standard peak molecular weights of styrene are converted to polyethylene molecular weights using the following equation (as described in the Publication of

Williams and Ward, J. Polym. Sci., Polym. Let.,

Mpolyethylene = A (Mpolistinerene) B

<img file="MX347015B_D0025.tif" />

<img file="MX347015B_D0026.tif" />

Here, B has a value of 1.0, and the experimentally determined value of A is 0.38.

A first order polynomial was used to fit the respective polyethylene equivalent calibration points obtained from equation (1) to their observed elution volumes. The actual polynomial fit was obtained so that the logarithm of the equivalent molecular weights of polyethylene is related to the observed elution volumes (and associated powers) for each polystyrene standard.

The number, weight, and z-average molecular weights were calculated according to the following equations:

_ Σ ^ _ Σ ^ · * ^)

Μη = ——------- Mw: ---- &lt; ₍₂₎ (3)

Mz = —------ (4)

Where, Wfi is the fraction of the i-th component by weight and Mi is the molecular weight of the i-th component.

MWD was expressed as the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn).

MEXICAN INSTITUTE

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An A value was determined by adjusting the vSfS'K '¹ A ^ STTia equation (1) to Mw, the molecular weight Γ ”Ρi * мédTo in weight was calculated using equation (3) and the corresponding retention volume polynomial, according to the independently determined Mw value obtained according to with the linear homopolymer reference with the known weight average molecular weight of 115,000 g / mol.

Trisubstituted Unsaturation Group Determination Method (FTIR)

The pellets were first pressed to make a 0.25mm thick film and then again pressed to make a 0.125mm thin film. The film was subsequently secured on a scan card, and both sides were subsequently sandblasted before loading onto a Nicolet 6700 FTIR instrument. The area under peak at 909 cm '¹ was integrated to obtain the value of the number of trisubstituted unsaturation units per 1,000,000 carbons using 64 scans with a resolution of 2 cm '¹. This technique has been calibrated using a known absorbance and concentration, and is corrected for film thickness to determine the concentration of the sample.

Film Testing Conditions

The following physical properties are measured on the films produced:

2%

Secant

Modulus-MD (address of

<img file="MX347015B_D0027.tif" />

(cross direction): ASTM D882-10 (Average Ha_five film samples in each direction, each sample "1 inch (2.54 cm) x 6 inches (15.24 cm)".

Elmendorf MD and CD Tear Strength: ASTM D 1922-09 (average of 15 film samples in each direction; each sample “3 inches (7.62 cm) x 2.5 inches (6.35 cm)” in a crescent shape). Films of the present invention preferably have an MD tear greater than 100g, more preferably greater than 200g, and a CD tear greater than 700g.

MD and CD Tensile Strength: ASTM D882-10 (average of five film samples in each direction; each sample 1 inch (2.54 cm) x 6 inches (15.24 cm).

Dart Impact Resistance: ASTM D1709-09 (minimum of 20 drops to achieve 50% failure, typically ten "10-inch (25.4 cm) x 36-inch (91.44 cm)" strips.

Puncture Resistance: Puncture is measured on an INSTRON Model 4201 with SINTECH SOFTWARE

TESTWORKS Version 3.10. The sample size is "6 inches (15.24 cm) x 6 inches (15.24 cm)" and six measurements were made to determine an average puncture value. The film is conditioned for 4 hours after film production, and at least 24 hours in an ASTM controlled laboratory (temperature 23 ° C and 50% fr humidity

IMPI ^^

ΙΝΓΓΠνΤΟ MUUCANV relative). A 10 ^ 1 ^ 7 ^ 9-3 ^ 432 ^ load cell is used with a 4 inch (10.16 cm) diameter fastener. The lancing probe is a polished stainless steel ball with a “diameter of¹Λ inch (1.27 cm) ”on a 2.5” (6.35 cm) rod with a “maximum stroke length of 7.5 inches (19.05 cm).”

There is no gauge length, and the probe is as close as possible but not touching the sample (the probe is adjusted by lifting the probe until it touches the sample). The probe is then gradually lowered, until it no longer touches the sample. The transverse head is subsequently adjusted to zero. Considering the maximum distance, the distance can be approximately 0.10 inch (0.254 cm). Crosshead speed is 10 inches / minute (25.4 cm / min). The thickness is measured in the middle of the sample. The thickness of the film, the distance traveled of the transverse head, and the peak load are used to determine the puncture using the software. The lancing probe is cleaned using a "KIMWIPE" after each test.

Examples

The two examples described below are for two groups of resins, each having a similar molecular weight, with different concentrations of an alkoxyamine derivative additive. The specific additive used is oct decane 9- (acetyloxy) -3,8,10-triethyl-7,8,10-trimethyl-1,527 dioxa-9-azasp¡ro [5.5] undec-3-¡l] met What the^neither'' ^ NDUSnUA¹ a master batch LDRE (resin D) that has less than 1% by weight of the additive, in this example it has the U.b8^b/ or by weight of the additive. It should be noted that the ppm levels reported below refer to the amount of alkoxyamine derivative added and not to the amount of the entire master batch added.

The LDPE D resin and the alkoxyamine derivative additive are compounded in a Coperion Werner-Pfleiderer ZSK-30 (ZSK-30) intermesh 30mm twin screw extruder to form a master batch. The ZSK-30 has a ten barrel section with an overall length of 960mm and a length to diameter ratio of 32 (L / D). A two-hole strand die is used without a breaker plate or strainer gasket. The extruder consists of a DC motor, connected to a gearbox by V bands. The 15 Hp motor is energized through a GE adjustable speed drive located in a control cabinet. The screw shaft speed control range is 1:10. The maximum screw shaft speed is 500 revolutions per minute. A pressure transducer is placed on the front of the die to measure the pressure of the die.

The extruder has eight heated / cooled barrel sections along with a 30mm spacer, producing five temperature controlled zones. It has only one feeding section enfjuala ^^ úAiGa4ren¿a

INSTITUTO MÍXIGaNC

DE LA MOREDA Γ a heated die section, which ¹ They are held together by tie rods and are 'supported on the machine frame. Each section can be electrically heated with angular half shell heaters and cooled through a special channel cooling system.

The screws consist of continuous shafts on which the wing screw components and special kneading elements are installed in any required order. The elements are held radially together through keys and slots, and axially through a screw-in screw tip. The bolt shafts connect to the gear shafts by coupling, and can be easily removed from the bolt barrel for removal.

A Conair pelletizer is used to pellet the blends. It is a solid 220 variable speed cutting unit. The variable speed motor operates a solid machined cutting wheel, which in turn operates a fixed metal roller. A movable rubber roller presses against the fixed roller and helps to pull the strands through friction on the cutter wheel. The tension on the movable roller can be adjusted as required.

The temperatures are adjusted in the feed zone, four zones in the extruder and the die as:

<td>Feeding:</td><td>80 ° C</td>

<td>Zone 1:</td><td>160 ° C</td>

<td>Zone 2:</td><td>180 ° C</td>

<td>Zone 3:</td><td>185 ° C</td>

<td>Zone 4:</td><td>190 ° C</td>

<td>Die:</td><td>210 ° C</td>

<img file="MX347015B_D0028.tif" />

The screw shaft speed is set at 276 revolutions per minute (RPM), resulting in an output range of approximately 52 Ib / hr (23.58 kg / hr).

The master batch defined above is dry blended with additional amounts of the LDPE D resin in order to bring the concentration of the alkoxyamine derivative to a desired level, so that when added in an amount of 3% by weight, in Compared to the target polyethylene, the target will be added in the amounts shown in the table. The master batch or dry blended material thereof is blended with LLDPE B or C resins, using the following configuration: The master batch or dry blended material is fed through a hopper into a single screw extruder of 2 inch (6.35 cm) Sterling, which is used on the side arm carrier with a 3200 psig (224.98 kg / cm) rupture disc²). The four heating zones in the single screw extruder are set at a temperature of 220 ° C.

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LLDPE resin B (Example 1) or C (E j βΊΜ1&gt; ΚΜ £), feed through another hopper into an AYtrusnr .Cantnry-7SK-40 (extruder with a 37.13 diameter length ratio, a screw extruder double 40 mm, intermesh, joint rotation with a transmission of 150 Hp drive, armature of 244 amps (maximum), and screw of 1200 rpm (maximum)). The nine heating zones in the extruder are set as follows: the first at a temperature of 25 ° C, the second at a temperature of 100 ° C, and the rest at a temperature of 200 ° C.

The polymer melt pump is a 100cc / rev Maag pump that helps transport the molten polymer from the extruder, and through the downstream equipment. It is powered by a 15 hp motor with a 20.55 / 1 reduction gear. The pump is equipped with a pressure transmitter and a 5,200 psi (365.59 kg./cm) rupture disc.²) on the inlet and outlet transition piece. There are heating zones in the melt pump, and inlet and outlet transition pieces which are adjusted to a temperature of 220 ° C.

The melt pump is attached to the extruder, and the flow from the single screw extruder enters the polymer stream through an injector from the side arm single screw extruder. The injector is a pipe with% inch (1.89 cm) protruding at the center line of the

IMPI '' 'STnVTOMEXKXNo pipe with an internal diameter of 3.1 inches (7.8 ^ &lt;rm ^.

<img file="MX347015B_D0029.tif" />

The polymer coming from the extruder, ce¹ combines — the resin from a single screw extruder as it flows through a static mixer with an 18 Kenics mixing element mixer with an internal diameter of 3.1 inches (7.87 cm). The mixing elements have a length to diameter ratio of 1.3. There are seven heating zones in the static mixer and all are set at a temperature of 220 ° C.

Subsequently the combined stream flows through a Gala pelletizer system. The Gala is equipped with a Gala 12 hole die (2.36mm hole diameter) with 4 of the holes plugged. The cutter has a 4 blade concentrator and operates at approximately 800 ppm. The temperature of the water inside the pelletizer is kept at 30 ° C.

The amount of the dry blended masterbatch or masterbatch and resin D is about 3% by weight of the total resin amount. The residence time of the master batch in the side arm extruder is approximately 20 minutes, and the residence time of the polymer in the static mixer is approximately 3 minutes.

The melt strength of each of these examples is measured using a Gottfert Rheotester 2000 at a temperature of 190 ° C. Viscosity is measured using a constant temperature of 190 ° C in a hnSfeF * scan on a TA Instruments "Advanced Rheometric Expansion System (ARES)". Melt indices are measured using ASTM D-1238 at a temperature of 190 ° C using a Tinius-Olsen Model MP987 extrusion plastomer. Molecular weights are determined using the method described under the Test Methods section above.

Description of the Resin:

Resin A (Dowlex 61528.20) is a Ziegler-Natta catalyzed polyethylene resin made in a solution process that has a Melt Index of 0.5 g / 10 minutes (at 190 ° C, 2.16 kg ASTM D-1238) and a 0.921 g / cm density³ (ASTM D792).

Resin B (Dowlex TG 2085B) is a Ziegler-Natta catalyzed polyethylene resin made in a solution process that has a melt index of 0.95 g / 10 minutes (at 190 ° C, 2.16 kg ASTM D-1238) and a density of 0.919 g / cm³ (ASTM D792).

Resin C (Dowlex NG 5085B) is a Ziegler-Natta catalyzed polyethylene made in a paste process that has a melt index of 1.3 g / 10 minutes (at 190 ° C, 2.16 kg ASTM D-1238) and a density 0.918 g / cm³(ASTM D792).

Resin D (LDPE 208C / 206M) is a homopolymer ethylene resin made in a tubuTaK ^ é ^^ i reactor that has a melt index of 0.7 g / 10 minutes (in

190 ° C, 2.16kg ASTM D-1238) and a density of 0.925 g / cm³ (ASTM D792).

Resin E (Dowlex 2045) is a Ziegler-Natta catalyzed polyethylene resin made in a solution process that has a melt index of 1.0 g / 10 minutes (at 190 ° C, 2.16 kg ASTM D-1238) and a density 0.920 g / cm³ (ASTM D792).

Resin F (LDPE 132i) is a homopolymer ethylene resin made in a high pressure tubular reactor that has a melt rate of 0.25 g / 10 min (at 190 ° C, 2.16 kg ASTM D-1238) and a density 0.922 g / cm³(ASTM D792).

Resin G (LDPE 204M) is a homopolymer ethylene resin made in a high pressure tubular reactor that has a melt index of 0.3 g / 10 minutes (at 190 ° C, 2.16 kg ASTM D-1238) and a density 0.920 g / cm³(ASTM D792).

The white masterbatch is a homopolymer ethylene resin made in a high pressure tubular reactor that has a melt rate of 13 g / 10 min (at 190 ° C, 2.16 kg ASTM D-1238) with 60% in TiO weight₂ in the form of a white pigment

The black masterbatch is a homopolymer ethylene resin made in a 3ervwMM * ^ eríS5 tubular reactor that has a melt index of 13 g / 10 minutesd (in

190 ° C, 2.16 kg ASTM D-1238) with 60% by weight of carbon black as the black coloring agent. Movie Production

Example 3

Films are made using resins produced in Examples 1 and 2 above in a 3.5 inch (8.89 cm) diameter Sterling extruder with a 30: 1 length to diameter ratio and a 6 inch (15.24 cm) die with a linear low density screw type (LLDPE) with internal as well as external cooling. Films are made from 100% of the samples in this example.

The general parameters of the blown film extruder used to produce the blown films for high LLDPE content films are shown in Table 1. All resins shown contain 3% by weight of resin D. The temperatures in Table 1 show the temperatures closest to the pellet hopper (Barrel 1) and in increasing order as the polymer is being extruded through the die (upper die). The film properties for some resins (control resin and of the respective present invention) are shown in Table 2.

Example 4

A target resin is produced by incorporating an alkoxyamine derivative additive in a two-way process.

<img file="MX347015B_D0030.tif" />

The specific used is 9- (acetyloxy) -3,8,10-triethyl-7,8,1O-trimethyl-1,5-dioxa-9-azaspiro [5.5] undec-3-yl] methyl octadecanoate, which is added in the form of a master batch LDPE (resin

D) that has less than 1% by weight of the additive, in this example it has 0.1520% by weight of the additive.

A concentrate with LDPE resin and D the alkoxyamine derivative additive is first made in a Coperion Werner-Pfleiderer ZSK-30 (ZSK-30) intermesh 30mm twin screw extruder to form the master batch. The ZSK-30 has ten barrel sections with an overall length of 960mm, and a length to diameter ratio of 32 (L / D). A two-hole strand die is used without a breaker plate or strainer packing. The extruder consists of a DC motor, connected to a gearbox by V-bands. The 15 Hp motor is powered by a GE adjustable speed transmission located in a control cabinet. The screw shaft speed control range is 1:10. The maximum screw shaft speed is 500 revolutions per minute. A pressure transducer is placed on the front of the die to measure pressure.

The extruder has eight heated / cooled barrel sections along with a 30mm spacer, producing five temperature controlled zones. It has only one cooling feed section and a heated die section, which are held together by tie rod and supported on the machine frame. Each section can be electrically heated with angled half shell heaters and can be cooled through a special system of cooling channels.

The screws consist of continuous shafts into which the finned screw components and the special kneading elements are installed in any order. The elements are held together radially through keys and slots, and axially through a screw-in screw tip. The bolt shafts are connected to the gear shafts by couplings, and can be easily removed from the bolt barrel for dismantling.

A Conair pelletizer is used to pellet the blends. It is a solid 220 variable speed cutting unit. The variable speed motor operates a solid machined cutting wheel, which in turn, operates a fixed metal roller. A movable rubber roller presses against the fixed roller and helps to pull the strands through friction on the cutter wheel. The tension on the movable roller can be adjusted as required.

Temperatures are set in the feed zone, 4 zones in the extruder, and the die in form d:

<img file="MX347015B_D0031.tif" />

IMPI mhuwswm *

Power supply: 80 ° C

Zonal: 160 ° C

<td>Zone 2:</td><td>160 ° C</td>

<td>Zone 3:</td><td>160 ° C</td>

<td>Zone 4:</td><td>160 ° C</td>

<td>Die:</td><td>160 ° C</td>

The screw date speed is set at 275 revolutions per minute (RPM), resulting in an output range of 50 Ib / hr (22.67 kg / hr).

The aforementioned concentrate is further incorporated into resin E, using 4% by weight of the concentrate to produce the target resin E with 60 parts per million by weight of the additive. For this compound generation step, a Leistritz co-rotating twin screw extruder is used, with a length to diameter ratio of 40 and a screw diameter of 75 mm. The maximum output is 600kg per hour. There are eight heating zones on the extruder, and two heating zones on the die as follows:

<td>Feeding:</td><td>80 ° C</td>

<td>Zone 1:</td><td>180 ° C</td>

<td>Zone 2:</td><td>190 ° C</td>

<td>Zone 3:</td><td>200 ° C</td>

<td>Zone 4:</td><td>200 ° C</td>

<td>Zone 5:</td><td>210 ° C</td>

<td>Zone 6:</td><td>220 ° C</td>

<td>Zone 7:</td><td>220 ° C</td>

<td>Zone 8:</td><td>220 ° C</td>

<td>Die zone 1:</td><td>220 ° C</td>

<td>Die Zone 2:</td><td>220 ° C</td>

IMPI

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<img file="MX347015B_D0032.tif" />

To pelletize the resin, a Gala submerged pelletizer with 2500 rpm and a water temperature of 30 ° C is used.

The target resin compounded as described above is referred to as resin E with 60 ppm additive.

Films are made using a typical Silobag extrusion machine and a three-layer blown film line with a layer distribution of 55% / 27% / 18%, with corresponding screw diameters of 150/120/90 mm; the center screw has a typical LDPE screw and a die diameter of 43 inches (109.22 cm). BUR is 2.5: 1, with internal bubble cooling and machine output of 950 to 1050 kg / hr. The

<img file="MX347015B_D0033.tif" />

film thickness is 235 microns. The formffUfói ^ Kdj »DE LA n &lt;» ltt&gt; AP INDUSTRIAL has an overall proportion of 52.02% resin G (LDPE

204Μ) and 33.20% E resin, the rest of the formulation (14.78%) being composed of white or black master batches and waste from the process. In none of the master batches or scrap types of materials or proportions thereof, are they changed during testing.

The materials are distributed in the three layers as follows:

Layer A (55%): 54% Resin G + 35% Resin E + 11% Master Batch white color

Layer B (27%): 57% Resin G + 15% Resin E + 28% Waste

Layer C (18%): 38.5% Resin G + 55% Resin E + 6.5% of Master Batch color Black.

The experiments are carried out by replacing the standard LLDPE resin E with LLDPE with a high melt resistance (Resin E + 60 ppm additive). Case 1 is used as a control. Cases 2 and 3 are designed to test bubble stability with fed amounts of LLDPE resin.

Case # 1: all the resin E on the outer skin (Layer A) is replaced by the target resin E made in composite at a temperature of 235 ° C with 60 ppm of the additive. The amperage increases the temporality in this extruder, but it does reduce

IMPI ^ gently on the original level and bubble stability was obtained. This is the control case, and is used to verify that there are no variations when compared to the standard LLDPE case.

Case # 2: The formulation is changed in Layer A, replacing resin E with resin E made in compound with 60 ppm of additive, increasing this resin by 15%, and correspondingly reducing resin G. The amperage increases from 81 to 100, exceeding the safety limit of this extruder. Increase the temperature profile by 10-15 ° C to reduce amperage. This is used as an intermediate step to determine the limit of this extruder when a part of the resin E is replaced in one of the three layers.

Case # 3: the same formulation as in Case # 2, but also, 10% of the resin E in Layer C is replaced by the resin E made in compound with 60 ppm of additive. The pressure increases until the limit of the machine is reached, and is the final formulation. Good bubble stability is achieved with the new formulation. The final improved formulation is:

Layer A (55%): 39% Resin G + 50% Resin E + 60 ppm of additive + 11% of the white master batch.

Layer B (27%): 57% Resin G + 15% Resin E + 28% D s cho.

IMPIAS

Layer C (18%): 38.5% Resin G + 45%

INDUSTRIAL (Resin E + 60 ppm additive) + 6.5% of black master batch.

The effect of the increase in the LLDPE portion can be observed through mechanical property measurements. The results are described in Table 3. Elmendorf Tear MD, is an important property for the application, and increases by 13% as the ratio of LLDPE to LDPE is increased in the combination. The test results at the end show that LLDPE made from a compound with the additive can provide better mechanical properties without losing bubble stability, and therefore maintain the same machine production.

Figure 1 shows the curve of resistance to melting versus stretching speed with increasing additive concentration. The incorporation of the additive changes the behavior of resin B, increasing the force necessary to stretch the molten polymer. All samples are made in composite with the indicated resins with 3% by weight of resin D.

Figure 2 shows the viscosity versus the frequency of the cut-off range measured using a constant temperature of 190 ° C in a frequency sweep in a TA Instruments "Advanced Rheometric Expansion System" (ARES) ". The incorporation of the additive changes the behavior of resin C in ranges of

IMPI

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<img file="MX347015B_D0034.tif" />

resins contain 3% by weight of resin D. Figure 3 shows the melt strength of the combinations of the resin of the present invention and the comparative resin, versus the amount of F LDPE resin. For LDPE amounts in the blend less than 50% by weight, the resin of the present invention without additive exhibits a higher melt resistance than the comparative resin without additive. Both resin samples contain 3% by weight of D LDPE resin.

Table 1.

Process parameters

IMPI the pWBSS YesB

<img file="MX347015B_D0035.tif" />

used to produce all the movies. All resins also contain 3% of resin D.

<td>Description</td><td>Example 1 (Resin B + LDPE20 8C)</td><td>Example 1 + 30 ppm</td><td>Example 1 + 60 ppm</td><td>Example 2 (Resin C + LDPE20 8C)</td><td>Example 2 + 60 ppm</td><td>Example 2 + 80 ppm</td>

<td>Speed ​​(rpm)</td><td> 18.9</td><td> 18.9</td><td> 19.1</td><td> 18.1</td><td> 18.8</td><td> 18.8</td>

<td>Range (Ib / hr)</td><td> 152</td><td> 151</td><td> 151</td><td> 147</td><td> 151</td><td> 151</td>

<td>Range / rpm</td><td> 8.04</td><td> 7.99</td><td> 7.91</td><td> 8.12</td><td> 8.03</td><td> 8.03</td>

<td>Barrel P1 (psi)</td><td> 3010</td><td> 3210</td><td> 3120</td><td> 2590</td><td> 2770</td><td> 2840</td>

<td>Barrel P2 (psi)</td><td> 4190</td><td> 4370</td><td> 4370</td><td> 3510</td><td> 3730</td><td> 3840</td>

<td>Barrel P3 (psi)</td><td> 4410</td><td> 4570</td><td> 4680</td><td> 3590</td><td> 3870</td><td> 4040</td>

<td>Strainer P (psi)</td><td> 4320</td><td> 4450</td><td> 4580</td><td> 3500</td><td> 3790</td><td> 3950</td>

<td>Adapter P (psi)</td><td> 3040</td><td> 3080</td><td> 3190</td><td> 2370</td><td> 2610</td><td> 2670</td>

<td>Melting temperature (F)</td><td> 456</td><td> 457</td><td> 457</td><td> 457</td><td> 456</td><td> 457</td>

<td>Barrel T1 (F)</td><td> 378</td><td> 374</td><td> 375</td><td> 375</td><td> 375</td><td> 375</td>

<td>Barrel T2 (F)</td><td> 427</td><td> 420</td><td> 420</td><td> 420</td><td> 420</td><td> 420</td>

<td>Barrel T3 (F)</td><td> 396</td><td> 389</td><td> 390</td><td> 389</td><td> 390</td><td> 391</td>

<td>Barrel T4 (F)</td><td> 379</td><td> 375</td><td> 375</td><td> 375</td><td> 375</td><td> 377</td>

<td>Barrel T5 (F)</td><td> 381</td><td> 375</td><td> 375</td><td> 374</td><td> 375</td><td> 375</td>

<td>Strainer T (F)</td><td> 424</td><td> 440</td><td> 445</td><td> 444</td><td> 445</td><td> 446</td>

<td>T (F) adapter</td><td> 450</td><td> 450</td><td> 450</td><td> 450</td><td> 450</td><td> 450</td>

<td>Block T (F)</td><td> 456</td><td> 450</td><td> 450</td><td> 450</td><td> 450</td><td> 451</td>

<td>Lower die T (F)</td><td> 452</td><td> 450</td><td> 450</td><td> 450</td><td> 450</td><td> 450</td>

<td>Inner die T (F)</td><td> 191</td><td> 186</td><td> 189</td><td> 188</td><td> 185</td><td> 184</td>

<td>Upper die T (F)</td><td> 451</td><td> 452</td><td> 450</td><td> 450</td><td> 450</td><td> 450</td>

<img file="MX347015B_D0036.tif" />

IMPI

MUlCMKt INSTITUTE

Table 2. Properties of films produced in accordance with the standardized conditions — as far as

Table 1.

<td>Description</td><td>Resin B</td><td>Standard deviation</td><td>Resin B w / 60 ppm</td><td>Standard deviation</td><td>Resin C</td><td>Standard deviation</td><td>Resin C w / 80 ppm</td><td>Standard deviation</td>

<td>Index of Melt (g / 10 min)</td><td> 0.95</td><td> 0.05</td><td> 0.69</td><td> 0.05</td><td> 1.3</td><td> .05</td><td> 1.00</td><td> 0.05</td>

<td>Density (g / cm^s)</td><td> 0.91 9</td><td> 0.002</td><td> 0.919</td><td> 0.002</td><td> 0.918</td><td> 0.002</td><td> 0.918</td><td> 0.002</td>

<td>Melt resistance (cN @ Plateu)</td><td> 4.8</td><td></td><td> 6.4</td><td></td><td> 3.5</td><td></td><td> 5.5</td><td></td>

<td>Thickness (mil)</td><td> 1.43</td><td> 0.052</td><td> 1.37</td><td> 0.082</td><td>1.27j</td><td> 0.045</td><td> 1.42</td><td> 0.027</td>

<td>Puncture (ft * lb / in^TO3)</td><td> 113</td><td> 18</td><td> 130</td><td> 23</td><td> 120</td><td> 18</td><td> 125</td><td> 21</td>

<td>Dart (g)</td><td> 235</td><td></td><td> 235</td><td></td><td> 262</td><td></td><td> 283</td><td></td>

<td>2% CD modulus blotter (psi)</td><td> 2994 2</td><td> 1042</td><td> 29016</td><td> 494</td><td> 26129</td><td> 1312</td><td> 27033</td><td> 1292</td>

<td>2% MD modulus blotter (psi)</td><td> 2615 8</td><td> 806</td><td> 27241</td><td> 365</td><td> 24144</td><td> 469</td><td> 23560</td><td> 568</td>

<td>DC to tension</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Peak load (1bf)</td><td> 5.2</td><td> 1.2</td><td> 6.5</td><td> 0.4</td><td> 5.2</td><td> 0.4</td><td> 5.3</td><td> 0.9</td>

<td>Deformation on interruption (%)</td><td> 604</td><td> 36</td><td> 634</td><td> 17</td><td> 624</td><td> 5</td><td> 603</td><td> 40</td>

<td>Tension in performance (psi)</td><td> 1581</td><td> 39</td><td> 1599</td><td> 72</td><td> 1544</td><td> 16</td><td> 1521</td><td> 40</td>

<td>Voltage MD</td><td></td><td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Peak Load (1bf)</td><td> 7.6</td><td> 1.1</td><td> 7.9</td><td> 1.0</td><td> 6.6</td><td> 0.8</td><td> 7.4</td><td> 1.0</td>

<td>Strain in tension (%)</td><td> 515</td><td> 22</td><td> 494</td><td> 14</td><td> 541</td><td> 15</td><td> 510</td><td> 39</td>

<td>Tension in performance (psi)</td><td> '161 9</td><td> 99</td><td> 1644</td><td> 40</td><td> 1590</td><td> 55</td><td> 1560</td><td> 142</td>

<td>Elmendorf MD tear (g)</td><td> 457</td><td> 64</td><td> 404</td><td> 58</td><td> 530</td><td> 83</td><td> 391</td><td> 92</td>

<td>Elmendorf Tear CD (g)</td><td> 884</td><td> 78</td><td> 931</td><td> 50</td><td> 807</td><td> 43</td><td> 897</td><td> 46</td>

Table 3 Mechanical properties of films

IMPI

<img file="MX347015B_D0037.tif" />

Silobag

<td></td><td colspan="2">Original formulation</td><td>Case # 3Me</td><td>Prayer formulation</td>

<td></td><td>Average</td><td>Standard deviation</td><td>Average</td><td>Standard deviation</td>

<td>Thickness (average)</td><td> 237</td><td> 5</td><td> 237</td><td> 6</td>

<td>Secant Modulus, 2%, MD, MPa</td><td> 190</td><td> 7</td><td> 189</td><td> 10</td>

<td>Secant Modulus, 2%, CD, MPa</td><td> 200</td><td> 2</td><td> 199</td><td> 3</td>

<td>Strength @ Break, MD, MPa</td><td> 26.8</td><td> ...</td><td> 26.7</td><td> ...</td>

<td>Elongation @ Break, MD,%</td><td> 1010</td><td> ...</td><td> 972</td><td> ...</td>

<td>Strength @ Yield, MD, MPa</td><td> 11.8</td><td> ...</td><td> 11.6</td><td> ...</td>

<td>Strength @ Break, CD, MPa</td><td> 24.7</td><td> ...</td><td> 25.7</td><td> ...</td>

<td>Elongation @ Break, CD,%</td><td> 1107</td><td> ...</td><td> 1098</td><td> ...</td>

<td>Strength @ Yield, CD, MPa</td><td> 11.4</td><td> ___</td><td> 11.6</td><td> ___</td>

<td>Elmendorf Tear, MD, g</td><td> 2149</td><td> 161</td><td> 2633</td><td> 186</td>

<td>Tearing Elmendorf, CD, g</td><td> &gt;3840</td><td> ...</td><td> &gt;3840</td><td> . ---</td>

The embodiments below are expressly considered part of the present invention, although each embodiment may not be claimed separately.

Although the present invention has been described in considerable detail throughout the foregoing description and examples, this detail is for the purpose of illustration and will not be construed as limiting the scope of the present invention, which is as stated. describes in the

IMPI¡ iMnVTUTO MUKAMC appended claims. All Northeast patents did SSP8

<img file="MX347015B_D0038.tif" />

Published patent applications and permitted patent aniiritndog Hp identified above are incorporated herein by reference.

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