Patent Application
20230036612
The present invention is related to a thermoplastic elastomer composition; and more specifically, the present invention is related to a thermoplastic elastomer composition such as an olefinic block copolymer (OBC) resin composition including (a) at least one thermoplastic elastomer blended with (b) at least one specific nucleation agent; and to a film made from the resin composition such that the film has an improvement in elastic performance (e.g., retractive force, hysteresis, and immediate set).
A thermoplastic elastomer such as an olefinic block copolymer (OBC) is known to provide a higher elasticity to a film structure compared to other polyolefins with the same crystallinity due to the OBC's unique molecular architecture. Because of OBC's unique molecular architecture, OBC has been used as the elastic component in film applications used to produce articles such as diaper and adult incontinence products because OBC has good processability. However, the film industry is still searching for a polyolefin film (e.g., a cast film) with improved elastic performance related to retractive force, hysteresis, and immediate set.
Various known resin compositions and processes have been described in the prior art. For example, U.S. Patent Application Publication No. US2015/0087758A1 discloses a resin composition including a polyolefin and other compounds such as a nucleation agent and an acid scavenger. The chemical formula of the nucleation agent is described in the above reference. The advantage of the resin composition is to improve physical properties of secant modulus in the machine direction (MD), tear strength in MD, clarity, and haze of a polyethylene blown film.
U.S. Patent Application Publication No. US2015/0086736A1 discloses a fabricated article made from a resin composition including: (1) a nucleation agent (the chemical formula is the same as the chemical formula described in US 2015/0087758 A1); and (2) a linear low polyethylene or a high-density polyethylene. The fabricated polyethylene article disclosed in the above reference is an extruded pipe.
DE 602004030248 D1 discloses a thermoplastic elastomer including an elastomeric phase, a thermoplastic phase, and a nucleation agent. The elastomer phase includes a rubbery styrenic copolymer or partially crosslinked ethylene-propylene diene; and the thermoplastic phase includes a propylene-based polymer. The nucleation agent is dispersed in the thermoplastic phase. The above reference discloses that the nucleation agent is used to enhance the crystal growth rate and clarity of the fabricated article made from the thermoplastic elastomer.
U.S. Patent Application Publication No. US2006/0199930A1 discloses OBC (e.g., INFUSE™, an OBC commercially available from The Dow Chemical Company); and the molecular architecture, the attributes, and the physical properties (e.g., elastic recovery, melting point, and the like.) of the OBC.
None of the above prior art references discloses a resin composition that improves the elastic performance (e.g., retractive force, hysteresis, and immediate set) of a cast film of OBC. It is desired, therefore, to provide a resin composition that includes (a) a thermoplastic elastomer such as OBC blended with (b) a specific nucleation agent; and such that the resulting resin composition improves the elastic performance of a cast film made from the resin composition.
The present invention is directed to a thermoplastic elastomer resin composition including (a) a thermoplastic elastomer such as OBC; and (b) a specific nucleation agent (or nucleating agent) blended with the thermoplastic elastomer, component (a); and such that the use of the resulting blended resin composition improves the elastic performance (e.g., physical properties of elasticity such as retractive force, hysteresis, and immediate set) of a cast film made from the above resin blend composition. In a preferred embodiment, the present invention includes an OBC-containing resin composition and a cast film made from the OBC-containing resin composition. The cast film made from the OBC-containing resin composition advantageously exhibits improved physical properties of elasticity when the OBC-containing resin composition and the specific nucleation agent is used to manufacture the cast film.
In one embodiment, the present invention includes a thermoplastic elastomer resin composition comprising:
wherein R1 is selected from the group consisting of a cyclopentyl group and moieties conforming to the structure of Formula (A); R2 is selected from the group consisting of hydrogen and a hydroxyl group; Formula (A) is:
R3 is selected from the group consisting of hydrogen, a halogen, methoxy, and phenyl; x is a positive integer; each M1 is a metal cation; y is the valence of the cation; z is a positive integer; b is zero or a positive integer; when b is a positive integer, each Q1 is a negatively-charged counterion and a is the valence of the negatively-charged counterion; and the values of x, y, z, a, and b satisfy the equation: x+(ab)=yz.
In another embodiment, the present invention includes an elastic film comprising at least one layer, wherein the at least one layer is formed from the above thermoplastic elastomer resin composition.
The above novel thermoplastic elastomer resin composition of the present invention has several advantages compared to known resin compositions of the prior art. For example, an OBC-containing resin composition of the present invention improves the elastic performance of a cast film made from the above OBC-containing resin composition. For example, an OBC-containing resin composition of the present invention provides an elastic film that has: (1) a retractive force percent change of, for example, at least 5%, (2) a hysteresis percent change of, for example, at least 3%, and (3) an immediate set percent change of, for example, at least 7% when such properties are compared to the same properties of another same film having no nucleation agent.
As used throughout this specification, the abbreviations given below have the following meanings, unless the context clearly indicates otherwise: “=” means “equal to”; @ means “at”; “<” means “less than”; “>” means “greater than”; “≥” means “greater than or equal to”; “≤” means “less than or equal to”; g=gram(s); g/10 min=gram(s) per 10 minutes; mg=milligram(s); kg=kilograms; kg/m3=kilograms per cubic meter; kg/hr=kilograms per hour; L=liter(s); mL=milliliter(s); mL/min=milliliter(s) per minute; g/L=grams per liter; RPM=revolutions per minute; Mw=molecular weight by weight; m=meter(s); Mn=number average molecular weight; Mw/Mn=molecular weight distribution; μm=microns: μL=microliters; mm=millimeter(s); cm=centimeter(s); min=minute(s); s=second(s); hr=hour(s);
° C.=degree(s) Celsius; mPa·s=millipascals-seconds; kPa=kilopascals; Pa·s/m2=pascals-seconds per meter squared; mg KOH/g=hydroxyl value in terms of milligrams of potassium hydroxide per gram of polyol; cells/mm2 is pore density value in terms of the number of cells per millimeter squared; %=percent, vol %=volume percent; and wt %=weight percent.
All percentages stated herein are weight percentages (wt %), unless otherwise indicated.
Temperatures are in degrees Celsius (° C.), and “ambient temperature” means between 20° C. and 25° C., unless specified otherwise.
In one broad embodiment, the present invention includes a thermoplastic elastomeric resin composition including: (a) at least one thermoplastic elastomer; and (b) at least one nucleation agent (or nucleating agent).
Thermoplastic elastomers include, for example, block copolymers; polyolefin elastomers (POE); and mixtures thereof. The block copolymers can include, for example, (ai) olefinic block copolymer (OBC); (aii) styrene block copolymers (SBC); and mixtures thereof.
The olefinic block copolymers (OBC) are a family of known polyethylene interpolymers containing high density “hard blocks” and low density “soft blocks” and are produced, for example, in a conventional single loop reactor in the presence of two or more catalysts and a chain shuttling agent. In one embodiment, the OBC useful in the present invention is, for example, polyethylene block copolymer. In another embodiment, the OBC useful in the present invention can include commercially available compounds such as INFUSE™ 9100, INFUSE™ 9500, INFUSE™ 9000 and INFUSE™ 9507 (available from The Dow Chemical Company).
The OBC useful in the present invention can include a block copolymer having several beneficial properties. For example, the density of the OBC is generally from 0.855 g/cm3 to 0.890 g/cm3 in one embodiment; from 0.860 g/cm3 to 0.890 g/cm3 in another embodiment; and from 0.870 g/cm3 to 0.890 g/cm3 in still another embodiment, as measured by the method described, for example, in ASTM D792.
For example, the melt index (I2) of the OBC is generally from 0.5 g/10 min to 15 g/10 min in one embodiment; from 0.5 g/10 min to 9.0 g/10 min in another embodiment; and from 0.9 g/10 min to 6.0 g/10 min in still another embodiment, as measured by the method described, for example, in ASTM D1238.
For example, the OBC has a molecular weight distribution of Mw/Mn of generally greater than 1.0 but lower than 4.0 in one embodiment; from 1.5 to 3.0 in another embodiment; from 2.1 to 2.9 in still another embodiment, and from 2.3 to 2.7 in yet another embodiment; as measured by a GPC method described herein below.
For example, the OBC has at least one melting point (Tm, in ° C.) that corresponds to the following Equation (I):
Tm>−2002.9+4538.5*(density)−2422.2*(density)2 Equation (I).
In other embodiments, the OBC may comprise one or more hard blocks and one or more soft blocks. As is known in the art, a “hard block” is the segment of polyethylene with a low octene comonomer content and resulting in high crystallinity; and a “soft block” is the segment of polyethylene with a high octene comonomer content and resulting in low crystallinity. A description of hard and soft segments can be found, for example, in U.S. Patent Application Publication No. US2006/0199930 A1. For example, the weight percent of the hard block in the OBC is from 5 wt % to 35 wt % in one general embodiment.
In one general embodiment, the concentration of the OBC used in the present invention is at least 75 wt %; at least 80 wt % in another embodiment, at least 85 wt % in still another embodiment, and at least 90 wt % in yet another embodiment, based on the total components of the resin composition. In other embodiments, the concentration of the OBC is, for example, from 75 wt % to 99.90 wt % in one general embodiment; from 80 wt % to 99.80 wt % in another embodiment, from 85 wt % to 99.5 wt % in still another embodiment; and from 85 wt % to 99.0 wt % in yet another embodiment, based on the total components of the resin composition.
In another embodiment, the block copolymer can be styrene block copolymers (SBC) such as styrene-isoprene-styrene (SIS); styrene-butadiene-styrene (SBS); styrene-ethylene-butylene-styrene (SEBS); and mixtures thereof. In another embodiment, the SBC useful in the present invention can include commercially available compounds such as Kraton™ D series products; and Kraton™ G series products (available from Kraton Corporation Company).
In still another embodiment, the thermoplastic elastomer can be (aiii) polyolefin elastomers (POE) such as polyethylene elastomer; polypropylene elastomer; and mixtures thereof. In another embodiment, the polyolefin elastomer useful in the present invention can include commercially available compounds such as AFFINITY™ EG 8200G, AFFINITY™ 8852G VERSIFY™ 3300 (all available from The Dow Chemical Company); and mixtures thereof.
The polyolefin elastomer useful in the present invention can include an elastomer having several beneficial properties. For example, the density of the polyolefin elastomer is generally from 0.855 g/cm3 to 0.890 g/cm3 in one embodiment; from 0.860 g/cm3 to 0.890 g/cm3 in another embodiment; and from 0.870 g/cm3 to 0.890 g/cm3 in still another embodiment, as measured by the method described, for example, in ASTM D792.
For example, the melt index (I2) of the polyolefin elastomer is generally from 0.5 g/10 min to 15 g/10 min in one embodiment; from 0.5 g/10 min to 9.0 g/10 min in another embodiment; and from 0.9 g/10 min to 6.0 g/10 min in still another embodiment, as measured by the method described, for example, in ASTM D1238.
In one general embodiment, the concentration of the polyolefin elastomer used in the present invention is at least 75 wt %; at least 80 wt % in another embodiment, at least 85 wt % in still another embodiment, and at least 90 wt % in yet another embodiment, based on the total components of the resin composition. In other embodiments, the concentration of the polyolefin elastomer is, for example, from 75 wt % to 99.90 wt % in one general embodiment; from 80 wt % to 99.80 wt % in another embodiment, from 85 wt % to 99.5 wt % in still another embodiment; and from 85 wt % to 99.0 wt % in yet another embodiment, based on the total components of the resin composition.
The nucleation agent, component (b), useful in the present invention includes, for example, at least one nucleation agent having the following general chemical Structure (I):
wherein R1 in Structure (I) above is selected from the group consisting of a cyclopentyl group and moieties conforming to the chemical structure of Formula (A); R2 is selected from the group consisting of hydrogen and a hydroxyl group; wherein Formula (A) is:
wherein R3 in Formula (A) above is selected from the group consisting of hydrogen, a halogen, methoxy, and phenyl; x is a positive integer; wherein each M1 in Structure (I) above is a metal cation; y is the valence of the cation; z is a positive integer; b is zero or a positive integer; when b is a positive integer, each Q1 is a negatively-charged counterion and a is the valence of the negatively-charged counterion; and the values of x, y, z, a, and b satisfy the equation: x+(ab)=yz.
Exemplary of the nucleation agent which fall within the scope of Structure (I) above, include one or more of the following chemical compounds:
and
In a preferred embodiment, the nucleation agent may include, for example, sodium salt of 4-chlorophenylamido-benzoic acid having the following structure:
In another preferred embodiment, the nucleation agent can include commercially available compounds such as HYPERFORM®HPN 210M (available from Milliken Chemical).
In one general embodiment, the concentration of the nucleation agent used in the present invention is from 0.1 wt % to 1 wt % (from 1,000 ppm to 10,000 ppm); from 0.1 wt % to 0.5 wt % (from 1,000 ppm to 5,000 ppm) in another embodiment; and from 0.15 wt % to 0.5 wt % in still another embodiment, based on the total components of the resin composition.
The thermoplastic elastomer (e.g., olefinic block copolymer) useful in the present invention includes, for example, small amounts of optional additives including plasticizers; stabilizers including viscosity stabilizers and hydrolytic stabilizers; primary and secondary antioxidants; ultraviolet light absorbers; anti-static agents; dyes, pigments, or other coloring agents; processing aids; slip additives; anti-block agents such as silica or talc; release agents; tackifying resins; or combinations of two or more of the optional components described above. In a preferred embodiment, the olefinic block copolymer may include, for example, one or more of the following optional additives: primary and secondary antioxidants; anti-block agents; and slip additives.
The nucleation agent useful in the present invention may also include an optional additive such as zinc stearate.
Generally, the thermoplastic elastomer resin composition is produced by mixing, blending (e.g., by dry blending via a tumbler blender) or compounding the thermoplastic elastomer and the nucleation agent together using conventional mixing methods and equipment known to those skilled in the art of mixing materials. For example, the nucleation agent is added to the thermoplastic elastomer as the thermoplastic elastomer is blended using a twin-screw extruder mixer such as a ZSK-26 twin screw extruder available from Coperion GmbH. While not limited to any particular screw extruder, in one embodiment, the ZSK-26 twin extruder has the following specifications: The barrel length of the ZSK-26 twin screw extruder is 100 mm per barrel; and 15 barrels comprises the entire process section of the extruder. The screw diameter of the extruder is 25.5 mm; and the screw has a flight depth of 4.55 mm. The feed rate of feed material to the extruder is 10 lbs/hr (4.54 kg/hr), and the rotation of the screw is 200 RPM. The melt temperature in the extruder is maintained at a temperature of from 120° C. to 130° C.
In one embodiment of the present invention, the process for making the composition includes, for example, compounding the nucleation agent and the thermoplastic elastomer (e.g., OBC) in a twin-screw extruder including passing a feed material at least one time through the extruder and two or more times through the extruder in another embodiment to make a masterbatch. Then, the masterbatch is dry blended with the thermoplastic elastomer (e.g., OBC) to make the final composition. For example, a masterbatch of the nucleation agent and the thermoplastic elastomer (e.g., OBC) is compounded using an extruder by first feeding 15 wt % of the nucleation agent and 85 wt % of the thermoplastic elastomer (e.g., OBC) as the feed materials in a first pass through the extruder resulting in a first compounded sample exiting the extruder. Then, in a second pass through the extruder, 33 wt % of the first compounded sample from the first pass is fed back into the twin extruder with 67 wt % of the same the thermoplastic elastomer (e.g., OBC) used in the first pass resulting in a second compounded sample exiting the extruder such that after the second pass, the compounded sample has a concentration of nucleation agent of 5 wt % in the thermoplastic elastomer (e.g., OBC). Then, the masterbatch is dry blended with the thermoplastic elastomer (e.g., OBC) to make the final composition, for example and not to be limited thereby, 96 wt % of the thermoplastic elastomer (e.g., OBC) is dry-blended with 4 wt % of the masterbatch to provide a composition of 2,000 ppm of the nucleation agent in the thermoplastic elastomer (e.g., OBC). The dry-blended composition can be fed into the extruder to fabricate the cast film. In an alternative embodiment, the nucleation agent can be added to the thermoplastic elastomer (e.g., OBC) in the form of a powder.
Some of the advantageous/beneficial properties exhibited by the final thermoplastic elastomer resin composition of the present invention produced according to the above-described process, includes, for example, a final resin composition having an improved: (1) hysteresis, (2) retractive force, and (3) immediate set of the cast film made from the above composition, compared to a film made from a resin composition without the nucleation agent
For example, the hysteresis property, in terms of percentage change in the property, exhibited by the composition of the present invention is generally in the range of from 3 to 15 in one embodiment; from 3.5 to 10 in another embodiment; and from 5 to 10 in still another embodiment. The hysteresis property is important and advantageous because the property maintains the elasticity of the film/sheet in applications where the film is used such as in diapers or adult incontinence articles.
For example, the retractive force property, in terms of percentage change in the property, exhibited by the composition of the present invention is generally in the range of from 3 to 15 in one embodiment; from 3 to 10 in another embodiment; and from 5 to 10 in still another embodiment. The retractive force property is important and advantageous because the property ensures that a diaper or an adult incontinence article stays firmly in place on a human body during body movement.
For example, the immediate set property, in terms of percentage change in the property, exhibited by the composition of the present invention is generally in the range of from 5 to 25 in one embodiment; from 5 to 20 in another embodiment; and from 5 to 15 in still another embodiment. The immediate set property is important and advantageous because the property prevents the slack of a diaper or an adult incontinence article after repeated stretch and release.
In general, once the thermoplastic elastomer resin composition is produced by mixing, blending or compounding the thermoplastic elastomer (e.g., OBC) and the nucleation agent together as described above, the resin composition can be used to form an elastic film member which can include one layer (a monolayer film) or two or more layers (a multilayer film). In a preferred embodiment, the elastic film comprising at least one layer, wherein the at least one layer is formed from the thermoplastic elastomer resin composition described above. The monolayer film and/or the multilayer film member can be further used to fabricate an elastic laminate member. In one embodiment, for example, the monolayer film and/or the multilayer film member can be laminated to a nonwoven substrate using conventional laminating processes.
In a broad embodiment, the monolayer film useful in the present invention includes, for example, an elastic film of one layer made from the thermoplastic elastomer resin composition described above. For example, the monolayer film can be made of an OBC (e.g., INFUSE™ 9100) as the thermoplastic elastomer. In a preferred embodiment, the elastic film of the present invention is a monolayer cast film or a blown film.
In another embodiment, the monolayer can be used as a first film layer and also include one or more other layers as a second layer to form a multilayer film structure. The second film layer can be made of, for example, polyethylene elastomer; polypropylene elastomer; styrene block copolymer; and mixtures thereof.
Generally, the film of the present invention is produced using the compounded thermoplastic elastomer (e.g., OBC) and nucleation agent resin composition described above, which is produced by mixing, blending or compounding the OBC and the nucleation agent together or dry blending the masterbatch and OBC as described above. For example, a monolayer of the film is produced using conventional processes and equipment known to those skilled in the art of fabricating films. In one embodiment, a conventional cast film process can be used to manufacture the film of the present invention. For example, a 3-layer cast film line (available from Collin) can be used to fabricate one or more monolayer cast films having a thickness of from 4.5 mil to 6.0 mil. While not limited to any cast film line, in one embodiment, the 3-layer cast film line has the following specifications: the cast film line includes two 25:1 L/D single screw extruders with a screw diameter of 20 mm (skin layers), and one 25:1 L/D single screw extruder with a screw diameter of 30 mm (core layer). The melt temperature of the extruders is at a temperature of from 230° C. to 240° C. The die gap of the extruders is 35 mil and the air gap of the extruders is from 1 inch (2.54 cm) to 1.5 inch (3.81 cm). The total output of the extruder is at about 4.77 kg/hr.
In one embodiment, the process includes preparing a predetermined amount of the masterbatch (nucleation agent plus olefinic block copolymer) as described above by dry-blending the masterbatch with a polymer material of the elastic monolayer film such as INFUSE™ 9100. Then, the dry-blended material is fed into all three extruders to provide a specific nucleation agent level in the fabricated cast film. For example, in one embodiment the nucleation agent level is at 2,000 ppm of HYPERFORM® HPN 210M.
Some of the advantageous/beneficial properties exhibited by the fabricated elastic monolayer film structure produced according to the above-described process, can include, for example: (1) an immediate set lower than 20%, as measured according to the Elasticity Test Method; (2) a hysteresis value of lower than 60%, as measured according to the Elasticity Test Method; and (3) a retractive force higher than 0.75 lbs (0.3409 kg).
For example, the film made with the composition containing the nucleation agent provides the film with several physical properties in terms of percentage change compared to a pure OBC that does not contain a nucleation agent, including (1) a retractive force percent change of at least 5% and some embodiments >5%; (2) an immediate set percent change of at least 7% and in some embodiments >7%; and/or (3) a hysteresis percent change of at least 3% and in some embodiments >3%; as compared to a same film having no nucleation agent.
The “percentage change of retractive force” can be calculated using the following equation:
The “percentage change of immediate set” can be calculated using the following equation:
The “percentage change of hysteresis” can be calculated using the following equation:
For example, retractive force percent change property of the monolayer film is from 3 to 15 in one embodiment; from 3 to 10 in another embodiment; and from 5 to 10 in still another embodiment.
For example, immediate set percent change property of the monolayer film is from 5 to 25 in one embodiment; from 5 to 20 in another embodiment; and from 5 to 15 in still another embodiment.
For example, hysteresis percent change property of the monolayer film is from 3 to 15 in one embodiment; from 3.5 to 10 in another embodiment; and from 5 to 10 in still another embodiment.
The above properties of immediate set, hysteresis, and retractive force are measured using an Elasticity Test Method. The Elasticity Test Method is generally performed using known equipment in the art such as an Instron instrument. The nominal gauge length of a specimen to be tested is 1 inch (2.54 cm) and the width of the specimen is 1 inch (2.54 cm). The load cell of the Instron is zeroed first and then the specimen is loaded carefully to the grip of the Instron to minimize any slack and pre-load stress. In one testing cycle (referred to as a loading and unloading process), the specimen is stretched to a strain of 100% at a speed of 125 mm/min (loading process). After reaching 100% strain, the specimen is held for 30 s; and then the specimen is returned to the zero-extension position at the speed of 125 mm/min (unloading process). The strain, at the point that the force reaches zero on the return step, is recorded as “immediate set”. The “retractive force” is obtained at 50% strain during the unloading step.
The hysteresis is calculated using the following equation:
The thickness of the monolayer film of the present invention, can be generally from 1 mil to 10 mil in one embodiment; and from 1 mil to 7 mil in another embodiment; and from 3 mil to 6 mil in still another embodiment.
In a preferred embodiment, the monolayer film or multilayer film described above can be used to make a laminate structure or member by laminating the monolayer film or multilayer film onto the surface of another substrate such as one or more of the following substrates: a nonwoven substrate; plastic, and mixtures thereof.
In a preferred embodiment, the laminate is made by any laminating process known in the art such as the process of stretched bonded laminate (SBL), neck bonded laminate (NBL), perforated film laminate (PFL), and ring roller.
The elastic film of the present invention can be used in applications where immediate, hysteresis, retractive force properties are desired including, for example, diapers, training pants, and adult incontinence products.
The following examples are presented to further illustrate the present invention in detail but are not to be construed as limiting the scope of the claims. Unless otherwise stated all parts and percentages are by weight.
Various terms and designations used in the Inventive Examples (Inv. Ex.) and the Comparative Examples (Comp. Ex.) which follow are explained hereinbelow:
“GPC” stands for gel permeation chromatography.
“DSC” stands for differential scanning calorimetry.
Various ingredients, components, additives, or raw materials used in the Inv. Ex. and the Comp. Ex. which follow are explained hereinbelow:
HYPERFORM® HPN-210M has the following chemical structure:
HYPERFORM® HPN-20E has the following chemical structure:
Millad® NX™ 8000 has the following chemical structure:
Polytetrafluoroethylene (PTFE) used in the examples has the following structure:
The compositions described in Table II were prepared as follows: A masterbatch of a nucleation agent and a thermoplastic elastomer, such as olefinic block copolymer, is compounded using an extruder by first feeding 15 wt % of the nucleation agent and 85 wt % of the olefinic block copolymer as the feed materials in a first pass through the extruder resulting in a first compounded sample exiting the extruder. Then, in a second pass through the extruder, 33 wt % of the first compounded sample from the first pass is fed back into the twin extruder with 67 wt % of the same olefinic block copolymer used in the first pass resulting in a second compounded sample exiting the extruder such that after the second pass, the compounded sample has a concentration of nucleation agent of 5 wt % in the olefinic block copolymer. Then the masterbatch is dry blended with the olefinic block copolymer to make the final composition. For example, 96 wt % of OBC is dry-blended with 4 wt % of the masterbatch to provide 2,000 ppm of the nucleation agent in OBC. The dry-blended composition can be fed into the extruder to fabricate the cast film.
The twin-screw extruder used for compounding is a ZSK-26 twin screw extruder (available from Coperion GmbH). The barrel length of the ZSK-26 twin screw extruder is 100 mm per barrel; and 15 barrels comprises the entire process section of the extruder. The screw diameter of the extruder is 25.5 mm; and the screw has a flight depth of 4.55 mm. The feed rate of feed material to the extruder is 10 lbs/hr (4.54 kg/hr), and the rotation of the screw is 200 RPM. The melt temperature in the extruder is maintained at a temperature of from 120° C. to 130° C.
The film structures described in Table III were manufactured using a cast film process. For example, a 3-layer cast film line (available from Collin) can be used to fabricate one or more monolayer cast films having a thickness of from 4.5 mil to 6.0 mil. While not limited to any cast film line, in one embodiment, the 3-layer cast film line has the following specifications: the cast film line comprises two 25:1 UD single screw extruders with a screw diameter of 20 mm (skin layers), and one 25:1 UD single screw extruder with a screw diameter of 30 mm (core layer). The melt temperature of the extruders is at a temperature of from 230° C. to 240° C. The die gap of the extruders is 35 mil and the air gap of the extruders is from 1 inch to 1.5 inch. The total output of the extruder is at about 4.77 kg/hr.
In one embodiment, the process includes preparing a predetermined amount of the masterbatch (nucleation agent plus olefinic block copolymer) as described above by dry-blending the masterbatch with a polymer material of the elastic monolayer film such as INFUSE™ 9100. Then, the dry-blended material is fed into all three extruders to provide a specific nucleation agent level in the fabricated cast film. For example, in one embodiment the nucleation agent level is at 2,000 ppm of HYPERFORM® HPN 210M.
Density measurements are performed using the procedure described in ASTM D792.
Melt index measurements are performed using the procedure described in ASTM D1238.
GPC measurements were performed using a chromatographic system consisting of a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler oven compartment was set at 160° C. and the column compartment was set at 150° C. The columns used were 4 Agilent “Mixed A” 30 cm 20-μm linear mixed-bed columns and a 20-μm pre-column. The chromatographic solvent used was 1,2,4 trichlorobenzene and contained 200 ppm of butylated hydroxytoluene (BHT). The solvent source was nitrogen sparged. The injection volume used was 200 μL and the flow rate was 1.0 m/min.
Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000 and were arranged in 6 “cocktail” mixtures with at least a decade of separation between individual molecular weights. The standards were purchased from Agilent Technologies. The polystyrene standards were prepared at 0.025 g in 50 mL of solvent for molecular weights 1,000,000, and 0.05 g in 50 mL of solvent for molecular weights <1,000,000. The polystyrene standards were dissolved at 80° C. with gentle agitation for 30 min. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using the following Equation I (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):
M_polyethylene=A×(M_polystyrene){circumflex over ( )}B (Equation I)
where M is molecular weight, A has a value of 0.4315 and B is equal to 1.0.
A fifth order polynomial was used to fit the respective polyethylene-equivalent calibration points. A small adjustment to A (from approximately 0.375 to 0.445) was made to correct for column resolution and band-broadening effects such that linear homopolymer polyethylene standard is obtained at 120,000 Mw.
The total plate count of the GPC column set was performed with decane (prepared at 0.04 g in 50 milliliters of trichlorobenzene and dissolved for 20 min with gentle agitation.) The plate count (Equation II) and symmetry (Equation III) were measured on a 200 μL injection according to the following equations:
Plate Count=5.54*(((RV_(Peak Max))/(Peak Width at ½ height)){circumflex over ( )}2 (Equation II)
where RV is the retention volume in milliliters, the peak width is in milliliters, the peak max is the maximum height of the peak, and ½ height is ½ height of the peak maximum.
where RV is the retention volume in milliliters and the peak width is in milliliters, Peak max is the maximum position of the peak, one tenth height is 1/10 height of the peak maximum, and where rear peak refers to the peak tail at later retention volumes than the peak max and where front peak refers to the peak front at earlier retention volumes than the peak max. The plate count for the chromatographic system should be greater than 18,000 and symmetry should be between 0.98 and 1.22.
Samples were prepared in a semi-automatic manner with the PolymerChar “Instrument Control” Software, wherein the samples were weight-targeted at 2 mg/ml, and the solvent (contained 200 ppm BHT) was added to a pre nitrogen-sparged septa-capped vial, via the PolymerChar high temperature autosampler. The samples were dissolved for 2 hr at 160° C. under “low speed” shaking.
The calculations of Mn(GPC), Mw(GPC), and Mz(GPC) were based on GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph according to Equations IV-VI, using PolymerChar GPCOne™ software, the baseline-subtracted IR chromatogram at each equally-spaced data collection point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve for the point (i) from Equation I.
In order to monitor the deviations over time, a flowrate marker (decane) was introduced into each sample via a micropump controlled with the PolymerChar GPC-IR system. This flowrate marker (FM) was used to linearly correct the pump flowrate (Flowrate (nominal)) for each sample by RV alignment of the respective decane peak within the sample (RV (FM Sample)) to that of the decane peak within the narrow standards calibration (RV (FM Calibrated)). Any changes in the time of the decane marker peak are then assumed to be related to a linear-shift in flowrate (Flowrate (effective)) for the entire run. To facilitate the highest accuracy of a RV measurement of the flow marker peak, a least-squares fitting routine is used to fit the peak of the flow marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation is then used to solve for the true peak position. After calibrating the system based on a flow marker peak, the effective flowrate (with respect to the narrow standards calibration) is calculated as Equation VII. Processing of the flow marker peak was done via the PolymerChar GPCOne™ Software. Acceptable flowrate correction is such that the effective flowrate should be within +/−1% of the nominal flowrate.
Flowrate(effective)=Flowrate (nominal)*(RV(FM Calibrated)/RV(FM Sample)) (Equation VII)
Differential scanning calorimetry (DSC) was performed on a TA Instruments Discovery DSC equipped with an RCS cooling unit and an autosampler. A nitrogen purge gas flow of 50 mL/min was used. The sample was pressed into a thin film at 190° C. on a Carver Hydraulic press. About 3-10 mg of material was cut from the pressed film, weighed, and placed in a light aluminum pan, and crimped shut. The thermal behavior of the samples was investigated using the following temperature profile: the sample was rapidly heated to 180° C. and held isothermally for 3 min. The sample was then cooled to −90° C. at 10° C./min and held isothermally for 3 min. The sample was then heated to 150° C. at 10° C./min. The cooling and second heading curves were used for analysis.
The Elasticity Test Method, described above, was performed using an Instron. The nominal gauge length of the specimen to be tested is 1 inch and the width of the specimen to be tested is 1 inch. The load cell was zeroed first and then the specimen was loaded carefully to the grip of Instron to minimize the slack and pre-load stress. In one testing cycle (called loading and unloading process), the specimen was stretched to the strain of 100% at the speed of 125 mm/min (loading process). After reaching 100% strain, the specimen was held for 30 s and then returned to the zero-extension position at the speed of 125 mm/min (unloading process). The strain at point the force reaches zero on the return step is recorded as immediate set. The retractive force is obtained at 50% strain during the unloading step. The hysteresis is calculated from the equation below.
The results of the Elasticity Test Method performed on the film samples in terms of “percentage change” of refractive force, immediate set and hysteresis are described in Table IV.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2020/058807 | 11/4/2020 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 62935848 | Nov 2019 | US |
