Patent Application
20170174852
Co-extrusion of multiple polymeric components into a single film is known in the art. For example, multiple polymeric flow streams have been combined in a die or feedblock in a layered fashion to provide a top to bottom multilayer film. It is also known to provide co-extruded film structures where the film is partitioned, not as coextensive layers in the thickness direction, but as stripes along the width dimension of the film. This has sometimes been called “side-by-side” co-extrusion. Extruded products with side-by-side oriented stripes are described, for example, in U.S. Pat. No. 4,435,141 (Weisner et al.), U.S. Pat. No. 6,159,544 (Liu et al.), U.S. Pat. No. 6,669,887 (Hilston et al.), and U.S. Pat. No. 7,678,316 (Ausen et al.) and Int. Pat. App. Pub. No. WO 2011/119323 (Ausen et al.). Films having multiple segmented flows within a matrix of another polymer are described, for example, in U.S. Pat. No. 5,773,374 (Wood et al.). In some cases, some of the stripes are elastic, and the resulting film is elastic in at least a direction transverse to the stripes.
In other technologies, apertured (e.g., macroporous) films are useful for a variety of applications. Macroporous, apertured films are commonly used for vapor and/or liquid permeable applications and have found use as components in personal hygiene articles (e.g., diapers and feminine hygiene products), filtering, and acoustic applications.
An example of a film having elastic segments side-by-side with inelastic segments, in which the elastic segments have apertures, is described in U.S. Pat. Appl. Pub. No. 2011/0160691 (Ng et al.).
Breathable elastic films having liquid barrier properties have long been a desire in the personal hygiene garment industry. Maintaining the liquid barrier properties upon stretching breathable elastic films has inherent difficulties since holes will also increase in area, degrading the barrier properties. The present disclosure provides a film having first and second segments along the film's width generally in a side-by-side fashion. The second segments are more elastic than the first segments. The first segments have a higher absorbance at a selected wavelength than the second segments. As a result, apertures can be preferentially formed through the first segments by a laser at the selected wavelength. Generally, when the film is stretched in the film's width direction, the apertures are not substantially stretched, and barrier properties can be maintained.
In one aspect, the present disclosure provides a film having first and second segments arranged along the film's width direction. The second segments are more elastic than the first segments. The first segments absorb light at a selected wavelength to a greater extent than the second segments. At least some of the first segments have apertures through their thicknesses, and a percentage of area of the first segments occupied by the apertures is greater than a percentage of area occupied by any apertures that may extend through the second segments. Typically, across at least a portion of the film's width the first and second segments alternate.
In another aspect, the present disclosure provides a laminate including such a film joined to a fibrous carrier.
In another aspect, the present disclosure provides an absorbent article including any of the embodiments of the aforementioned film or laminate.
In another aspect, the present disclosure provides a method of making the film. The method includes providing the film having first and second segments arranged along the film's width direction, in which the second segments are more elastic than the first segments, and forming apertures in at least some of the first segments using a laser at a selected wavelength. The first segments have a sufficient absorbance of light at the selected wavelength to form apertures therethrough. In other words, the first segments have a sufficient absorbance of light at the selected wavelength to reach the damage threshold. In some embodiments, the second segments have an insufficient absorbance at the selected wavelength to form apertures therethrough. In other words, in these embodiments, the second segments have an insufficient absorbance of light at the selected wavelength to reach the damage threshold.
The film according to and/or made according to the present disclosure has a significant amount of material that is relatively inelastic in combination with elastic material. For example, in some embodiments of any of the aforementioned aspects, the first segments make up a higher volume percentage than the second segments of the film. However, the films still have useful elongations. Therefore, in the films according to the present disclosure, relatively expensive elastic materials are used efficiently, and the films and articles made from them can be lower in cost than other elastic films, which typically include higher amounts of elastic materials.
Furthermore, since the first segments have a higher absorbance at a selected wavelength than the second segments, apertures can be selectively formed in the first segments using a laser at the selected wavelength. Since the first segments are relatively less elastic than the second segments, the apertures typically do not substantially change in shape or size when the film is stretched in a direction transverse to the direction in which the first and second segments extend. Therefore, the difference in moisture vapor transmission rate between a stretched and unstretched film is limited to the difference caused by thinning of the second segments when stretched and is much smaller than the difference in moisture vapor transmission rate of a stretched and unstretched film that has apertures in the elastic segments. This feature allows for more consistent moisture barrier properties when the film is incorporated in an absorbent article, for example.
In this application, terms such as “a”, “an” and “the” are not intended to refer to only a singular entity, but include the general class of which a specific example may be used for illustration. The terms “a”, “an”, and “the” are used interchangeably with the term “at least one”. The phrases “at least one of” and “comprises at least one of” followed by a list refers to any one of the items in the list and any combination of two or more items in the list. All numerical ranges are inclusive of their endpoints and non-integral values between the endpoints unless otherwise stated.
The term “alternating” as used herein refers to one first segment being disposed between any two adjacent second segments (i.e., the second segments have only one first segment between them) and one second segment being disposed between any two adjacent first segments.
The term “aperture” refers to a hole in the film. At least some portion of the aperture typically forms a straight pathway through the entire thickness of the film, which distinguishes these apertures from the tortuous pathways provided in microporous films. Apertures can have a generally tubular shape although this is not a requirement. In some embodiments, apertures may have a dimension (e.g., diameter or largest dimension) in the x-y plane of the film of at least 20, 25, 30, 35, or 40 micrometers. The apertures may have a dimension in the x-y plane of the film as large as the width of the first segments in any of the embodiments described below.
The term “elastic” refers to any material (such as a film that is 0.002 mm to 0.5 mm thick) that exhibits recovery from stretching or deformation. A material, film, or composition that is more elastic than another material, film, or composition exhibits at least one of higher elongation or lower hysteresis (usually both) than another material, film, or composition. In some embodiments, a material may be considered to be elastic if, upon application of a stretching force, it can be stretched to a length that is at least about 25 (in some embodiments, 50) percent greater than its initial length and can recover at least 40 percent of its elongation upon release of the stretching force.
The term “inelastic” refers to any material (such as a film that is 0.002 mm to 0.5 mm thick) that does not exhibit recovery from stretching or deformation to a large extent. For example, an inelastic material that is stretched to a length that is at least about 50 percent greater than its initial length will recover less than about 40, 25, 20, or 10 percent of its elongation upon release of its stretching force. In some embodiments, an inelastic material may be considered to be a flexible plastic that is capable of undergoing permanent plastic deformation if it is stretched past its reversible stretching region.
“Elongation” in terms of percent refers to {(the extended length−the initial length)/the initial length} multiplied by 100. Unless otherwise defined, when a film or portion thereof is said herein to have an elongation of at least 100 percent, it is meant that the film has an elongation to break of at least 100 percent.
The term “extensible” refers to a material that can be extended or elongated in the direction of an applied stretching force without destroying the structure of the material or material fibers. An extensible material may or may not have recovery properties. For example, an elastic material is an extensible material that has recovery properties. In some embodiments, an extensible material may be stretched to a length that is at least about 5, 10, 15, 20, 25, or 50 percent greater than its relaxed length without destroying the structure of the material or material fibers.
The term “machine direction” (MD) as used above and below denotes the direction of a running, continuous web during the manufacturing of the film disclosed herein. When a portion is cut from the continuous web, the machine direction corresponds to the longitudinal direction of the film. Accordingly, the terms machine direction and longitudinal direction may be used herein interchangeably. The term “cross-direction” (CD) as used above and below denotes the direction that is essentially perpendicular to the machine direction. When a portion of the film disclosed herein is cut from the continuous web, the cross-direction corresponds to the width of the film.
The term “incremental stretching” refers to a process of stretching a film, a fibrous material, or a laminate including a film and a fibrous material where the film, fibrous material, or laminate is supported at plural spaced apart locations during elongation, which restricts the elongation to specifically controlled increments of elongation defined by the spacing between support locations.
The terms “first”, “second”, and “third” are used in this disclosure. It will be understood that, unless otherwise noted, those terms are used in their relative sense only. For these components, the designation of “first”, “second”, and “third” may be applied to the components merely as a matter of convenience in the description of one or more of the embodiments.
The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The description that follows more particularly exemplifies illustrative embodiments. It is to be understood, therefore, that the drawings and following description are for illustration purposes only and should not be read in a manner that would unduly limit the scope of this disclosure.
The disclosure may be more completely understood in consideration of the following detailed description of various embodiments of the disclosure in connection with the accompanying drawings.
Referring now to
The second segments 4 of the film 1 are more elastic than the first segments 10. Therefore, when the film 1 is stretched in the “x” direction as shown in
In the film according to the present disclosure, the percentage of area of the first segments 10 occupied by the apertures therethrough (in other words, percent open area) is greater than the percent open area in the second segments 4. In some embodiments, the percentage of area of the first segments occupied by the apertures is at least 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 times greater than the percent open in the second segments. In some embodiments, the percentage of area of the second segments 4 occupied by apertures is not more than 1.0, 0.5, 0.25, or 0.1 percent. It is possible and typically desirable that the second segments 4 have no apertures and therefore have no open area.
Advantageously, apertures can be formed selectively in the first segments in films according to the present disclosure by designing the first segments to have a greater absorbance at a certain wavelength of light than the second segments. This allows apertures to be made with a laser without having to identify and specifically target the first segments with the laser. For example, in embodiments in which the laser would form apertures in both the first and second segments, the film would need to be aligned and indexed for each segment with the laser set to drill a column of apertures with a certain spacing. The aligning and indexing may be done manually or optically. A suitable mask may also be used over the second segments to prevent laser exposure in those segments. In contrast, when the first segments are designed to have a greater absorbance at the laser's wavelength than the second segments, the laser may be used without first identifying the first segments of the film. A point cloud array or any laser pattern can be used, and the laser will preferentially form apertures in the first segments.
Matching of laser and material can also be advantageous, for example, when the film to be apertured is a layer with a multilayer construction. Heating with the laser can be adjusted to a location of the film having first segments and second segments with the multilayer construction (e.g., multilayer film) or laminate as described below. For example, it can be advantageous to form apertures in a film disclosed herein when a fibrous layer is positioned between the laser and the film. In these embodiments, the first segments may be designed to have a greater absorbance at the laser's wavelength than the fibrous layer, and the fibrous layer may be selected to be minimally impacted by laser exposure. In some embodiments, the film to be apertured may also be positioned outside of the focal plane of the laser to adjust the level of heating.
In the method of making the film according to the present disclosure, apertures are formed with a laser. The laser may be any suitable laser operating at an infrared (IR), visible, and/or ultraviolet (UV) output wavelength.
Examples of suitable lasers include gas lasers, excimer lasers, solid state lasers, and chemical lasers. Examples of gas lasers include: carbon dioxide lasers (for example, those which produce power up to 100 kW at 10.6 micrometers); argon-ion lasers (for example, those which emit light at 458 nanometers (nm), 488 nm or 514.5 nm); carbon-monoxide lasers (for example, those which can produce power of up to 500 kW); and metal ion lasers, which are gas lasers that generate deep ultraviolet wavelengths. Helium-silver (HeAg) 224 nm lasers and neon-copper (NeCu) 248 nm lasers are two examples. These lasers have particularly narrow oscillation linewidths of less than 3 GHz (0.5 picometers).
Chemical lasers are powered by a chemical reaction, and can achieve high powers in continuous operation. For example, in the hydrogen fluoride laser (2700-2900 nm) and the deuterium fluoride laser (3800 nm), the reaction is the combination of hydrogen or deuterium gas with combustion products of ethylene in nitrogen trifluoride.
Excimer lasers are powered by a chemical reaction involving an excited dimer (that is, an “excimer”) which is a short-lived dimeric or heterodimeric molecule formed from two species (atoms), at least one of which is in an excited electronic state. They typically produce ultraviolet light. Commonly used excimer molecules include F2 (fluorine, emitting at 157 nm), and noble gas compounds (ArF (193 nm), KrCl (222 nm), KrF (248 nm), XeCl (308 nm), and XeF (351 nm)).
Solid state laser materials are commonly made by doping a crystalline solid host with ions that provide the required energy states. Examples include ruby lasers (for example, made from ruby or chromium-doped sapphire). Another useful type is made from neodymium-doped yttrium aluminum garnet (YAG), known as Nd:YAG. Nd:YAG lasers can produce high powers in the infrared spectrum at 1064 nm. Nd:YAG lasers are also commonly frequency doubled to produce 532 nm when a visible (green) coherent source is desired. Ytterbium, holmium, thulium, and erbium are other useful dopants in solid state lasers. Ytterbium is used in crystals such as Yb:YAG, Yb:KGW, Yb:KYW, Yb:SYS, Yb:BOYS, Yb:CaF2, typically operating around 1020 nm-1050 nm. They are potentially very efficient and high powered due to a small quantum defect. Extremely high powers in ultrashort pulses can be achieved with Yb:YAG. Holmium-doped YAG crystals emit at 2097 nm and form an efficient laser operating at infrared wavelengths strongly absorbed by water-bearing tissues. The Ho-YAG is usually operated in a pulsed mode. Titanium-doped sapphire (Ti:sapphire) produces a highly tunable infrared laser, commonly used for spectroscopy as well as the most common ultrashort pulsed laser. Solid state lasers also include glass or optical fiber hosted lasers, for example, with erbium or ytterbium ions as the active species.
In the method according to the present disclosure, the laser may be operated in pulsed and/or continuous wave mode. For example, the laser may operate at least partially in continuous wave mode and/or at least partially in pulsed mode. In some embodiments, the laser operates in pulsed mode. For a person skilled in the art, the suitable power for the laser, beam size on the material, and speed of the beam movement across the material can be adjusted to achieve the desired heating to form apertures.
The selected wavelength useful for the method and films according to the present disclosure can be any wavelength in a range from 180 nanometers (nm) to 1 millimeter (mm), in some embodiments, 200 nm to 100 micrometers or 200 nm to 11 micrometers. In some embodiments, the laser useful in the method disclosed herein is a UV laser, which, in some embodiments, produces light at one or more wavelengths in a range from 180 nm to 355 nm. In some embodiments, the laser is a 355 nm laser.
The first segments typically comprise a first polymeric composition, and the second segments comprise an elastic polymeric composition that is more elastic than the first polymeric composition. A number of useful additives can be included in the first polymeric composition so that it absorbs the selected wavelength to a greater extent than the elastic polymeric composition. Some useful additives include inorganic compounds such as oxides, hydroxides, sulfides, sulfates, and phosphates of metals such as copper, bismuth, tin, aluminum, zinc, silver, titanium, antimony, manganese, iron, nickel, and chromium and IR absorbing dyes.
In some embodiments, the selected wavelength is in the UV range, for example, in a range from 180 nm to 355 nm. Examples of useful additives that absorb UV light, which can be added to the first polymeric composition, include titanium dioxide, zinc oxide, antimony trioxide, calcium carbonate, and carbon black. In some embodiments, the first polymeric composition includes at least one of titanium dioxide or calcium carbonate. In some embodiments, the first polymeric composition includes titanium dioxide.
In some embodiments, the selected wavelength is in the infrared, in a range from about 700 nm to 1 mm, in some embodiments, about 700 nm to 20 micrometers or about 700 nm to 11 micrometers. Examples of useful additives that absorb IR light, which can be added to the first polymeric composition, include infrared-absorbing dyes from the classes of substances of the azo, azomethine, methine, anthraquinone, indanthrone, pyranthrone, flavanthrone, benzanthrone, phthalocyanine, perylene, dioxazine, thioindigo isoindoline, isoindolinone, quinacridone, pyrrolopyrrole or quinophthalone pigments and metal complexes of azo, azomethine or methine dyes or metal salts of azo compounds. Many of these dyes may be useful, for example, when the selected wavelength is about 1 micrometer.
In some embodiments, for example, when it is desirable to use a YAG laser, certain calcined powders of co-precipitated mixed oxides of antimony and tin (e.g., those described in U.S. Pat. No. 6,693,657 (Carroll, Jr., et al.) can be added to the first polymeric composition.
The first polymeric composition may include any of the additives in any of these embodiments at a higher concentration than the elastic polymeric composition. Or, in some embodiments, the elastic polymeric composition is free of any of these additives. Useful concentrations may be selected such that the first segments have a sufficient absorbance of light at the selected wavelength to reach the damage threshold, and the second segments have an insufficient absorbance of light at the selected wavelength to reach the damage threshold. The damage threshold is the point at which enough energy per unit area in the film has been absorbed to cause damage to the film structure. In some embodiments, the second segments may transmit light at the selected wavelength.
In some embodiments, to provide a segmented film wherein the first segments absorb light at a selected wavelength to a greater extent than the second segments, the first segments can be marked with a substance that absorbs at the selected wavelength. For example, if a carbon dioxide laser is used, and the selected wavelength is in a range from 9 to 11 micrometers, black marker or ink can be applied to the first segments on one or both surfaces of the film.
In some embodiments, to provide a segmented film wherein the first polymeric composition absorbs light at a selected wavelength to a greater extent than the elastic polymeric composition, an additive that is reflective at the selected wavelength can be incorporated into at least a portion of the second segments. For example, if a carbon dioxide laser is used, and the selected wavelength is in a range from 9 to 11 micrometers, silver particles or copper particles can be added to at least a portion of the second segments (e.g., into the elastic polymeric composition or to a skin layer of the second segments which may or may not include the elastic polymeric composition). Reflective particles may be useful in the second segments, for example, whether or not an absorbing additive is included in the first polymeric composition and/or whether or not the first segments are marked with an absorbing substance as described in any of the aforementioned embodiments.
Information regarding forming apertures in the first segments of films having first and second segments can be found in co-pending U.S. Pat. App. Ser. No. 61/974,877 (Hanschen et al.), filed on Apr. 3, 2014, and incorporated by reference herein in its entirety.
In films according to the present disclosure, a force required to stretch the second segments is typically less than a force required to stretch the first segments. The force required to stretch the first segments and the second segments can be compared, for example, by measuring the tensile modulus of the first polymeric composition and elastic polymeric composition, respectively. In some embodiments, the tensile modulus (i.e., the initial slope of the stress-strain curve) of the first segments is at least 2, 3, 5, 10, 20, 50, or 100 times the tensile modulus of the second segments. In some embodiments, it is readily visually determined whether the second segments can stretch more readily than the first segments. In some embodiments, the film disclosed herein has an elongation of at least 75 (in some embodiments, at least 100, 200, 250, or 300) percent and up to 1000 (in some embodiments, up to 750 or 500) percent) before plastic deformation of the first segments is observed.
In some embodiments, in films according to the present disclosure the apertures in the first segments do not substantially change in shape or size when the film is stretched in a direction transverse to the direction in which the first and second segments extend. In some embodiments, the phrase “do not substantially change” means that the apertures in the first segments have a first size (that is, a dimension in the x-y plane of the film in the direction of stretching) before stretching and a second size while stretching to 75% elongation, and the second size is less than 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 percent greater than the first size.
In some embodiments, films according to the present disclosure have a first moisture vapor transmission rate before stretching and a second moisture vapor transmission rate while stretching to 75% elongation, in which the second moisture vapor transmission rate is less than 50, 40, 30, 25, or 20 percent greater than the first moisture vapor transmission rate. When apertures are made in the second segments of the film, which typically stretch, the second moisture vapor transmission rate can be at least 100, 200, 300, 500, or 700 percent greater than the first moisture vapor transmission rate. The moisture vapor transmission rate in the film depends, among other things, the number of apertures that are formed in the film. In some embodiments, films according to the present disclosure have moisture vapor transmission rates of at least 100, 200, 400, 500, 800, or 1000 g/m2/day. Moisture vapor transmission rates can be measured according to the method provided in the Examples, below, or using ASTM E96-80.
The first segments and second segments in the film according to the present disclosure can have a variety of different structures. An end view of film according to the present disclosure is shown in
In the embodiment illustrated in
Other embodiments of films 400, 500 according to the present disclosure are shown in
Typically, in the embodiments illustrated in
In the embodiments shown in
The embodiments shown in
In the embodiments illustrated in
Another embodiment of a film according to the present disclosure is shown as an end view in
In film 600 shown in
Another embodiment of film according to the present disclosure is shown as an end view in
In many embodiments of the film according to the present disclosure, including the embodiments shown in
For any of the films 1, 100, 200, 300, 400, 500, 600, 700, each of the first polymeric composition and elastic polymeric composition is monolithic (that is, having a generally uniform composition) and would not be considered fibrous. Also, the layers (e.g., 208, 308, 408, 508), sheaths 608, and skin regions 708 would not be considered nonwoven materials. Generally, the first and second segments are co-extruded and melt bonded together. Furthermore, in any of the embodiments of films disclosed herein, the first and second segments are in the same layer in the thickness direction. That is, the first and second segments may be considered to occupy the same plane, or any imaginary line drawn through the film from one longitudinal edge to the opposite longitudinal edge would touch both the first and second segments. The films themselves are typically extruded as single-layer in the thickness direction although this is not a requirement.
Films comprising alternating first and second segments useful as apertured films according to the present disclosure can be made in a variety of ways. For example, a film 100 such as that shown in
In some embodiments, management of the flow of different polymer compositions into side-by-side lanes to form a film such as film 100 can be carried out using a single manifold die with a distribution plate such as that described in, for example, in U.S. Pat. Appl. Pub. No. 2012/0308755 (Gorman et al.), incorporated by reference herein in its entirety. In some of these embodiments, the die comprises a first die cavity in a first die portion, a second die cavity in a second die portion, a distribution plate interposed between at least a portion (e.g., most or all) of the first die cavity and at least a portion (e.g., most or all) of the second die cavity. The distribution plate has a first side forming a boundary of the first die cavity, a second side forming a boundary of the second die cavity, a dispensing edge, a plurality of first extrusion channels, and a plurality of second extrusion channels. The first extrusion channels extend from entrance openings at the first die cavity to exit openings on the dispensing edge, and the second extrusion channels extend from entrance openings at the second die cavity to exit openings on the dispensing edge. The exit openings of the first extrusion channels and the exit openings of the second extrusion channels are disposed in alternating positions along the dispensing edge. Each of the first extrusion channels comprises two opposite side walls and a joining surface connecting the two opposite side walls, and the joining surface of at least some of the first extrusion channels is typically substantially parallel to the first side of the distribution plate.
Films comprising alternating first and second segments useful for practicing the present disclosure such as film 100 shown in
Other side-by-side coextrusion techniques that may be useful for providing a film 100 such as that shown in
Films comprising alternating first and second segments useful as apertured films according to the present disclosure, such as the films illustrated in
The die may conveniently be comprised of a plurality of shims. The shims can include at least one first shim that provides a first fluid passageway and at least one second shim that provides a second fluid passageway from cavities within the die to the dispensing slot. The shim that provides the second fluid passageway may also provide at least one third fluid passageway. Each of the shims in the plurality of shims typically defines a portion of the dispensing slot. In some embodiments, the plurality of shims comprises a plurality of sequences of shims that includes shims where each sequence provides at least first and second fluid passageways between a first and a second cavity and the dispensing slot. In some of these embodiments, there will be additional shims that provide a passageway between a third (fourth, fifth, sixth, etc.) cavity and the dispensing slot. A subsequence of shims can form a layered second segment, which is bonded to a first segment on one or both sides. Some examples of useful shim sequences and subsequences will be discussed with more particularity below in connection with
In some embodiments, the shims will be assembled according to a plan that provides a sequence of shims of diverse types. Since different applications may have different requirements, the sequences can have diverse numbers of shims. The sequence may be a repeating sequence that is not limited to a particular number of repeats in a particular zone. Or the sequence may not regularly repeat, but different sequences of shims may be used. In one embodiment, a twelve-shim sequence that when properly provided with molten polymer forms a segment of film of a single-material alternating with a layered segment such as film 200 illustrated in
In some embodiments, the shims that provide a passageway between one cavity and the dispensing slot might have a flow restriction compared to the shims that provide a passageway between another cavity and the dispensing slot. The width of the distal opening within, for example, different shims of the sequence of shims, may be identical or different. For example, the portion of the dispensing opening provided by the shims that provide a passageway between one cavity and the dispensing slot could be narrower than the portion of the dispensing opening provided by the shims that provide a passageway between another cavity and the dispensing slot.
In some embodiments, extrusion dies described herein include a pair of end blocks for supporting the plurality of shims. In these embodiments it may be convenient for one or all of the shims to each have one or more through-holes for the passage of connectors between the pair of end blocks. Bolts disposed within such through-holes are one convenient approach for assembling the shims to the end blocks although the ordinary artisan may perceive other alternatives for assembling the extrusion die. In some embodiments, the at least one end block has an inlet port for introduction of fluid material into one or more of the cavities.
In some embodiments, the assembled shims (conveniently bolted between the end blocks) further comprise a manifold body for supporting the shims. The manifold body has at least one (or more (e.g., two or three, four, or more)) manifold therein, the manifold having an outlet. An expansion seal (e.g., made of copper or alloys thereof) is disposed so as to seal the manifold body and the shims, such that the expansion seal defines a portion of at least one of the cavities (in some embodiments, a portion of the first, second, and third cavities), and such that the expansion seal allows a conduit between the manifold and the cavity.
In some embodiments, the shims for dies described herein have thicknesses (in the narrowest dimension of the shim) in the range from 50 micrometers to 500 micrometers. Typically, the fluid passageways have dimension in the width direction of the extrusion die in a range from 50 micrometers to 750 micrometers, and heights corresponding to the thickness dimension of the film of less than 5 mm (with generally a preference for smaller heights for decreasingly smaller passageway widths), although widths and heights outside of these ranges may also be useful. In some embodiments, the fluid passageways can have heights in a range from 10 micrometers to 1.5 millimeters. For fluid passageways with large widths or diameters, several smaller thickness shims may be stacked together, or single shims of the desired passageway width may be used. Widths of first and second slot segments (described below for making first and second film segments) can correspond to the widths of the fluid passageways described above. The first and second slot segments may have widths within 10 percent of the widths of the fluid passageways.
The shims are tightly compressed to prevent gaps between the shims and polymer leakage. For example, 12 mm (0.5 inch) diameter bolts are typically used and tightened, at the extrusion temperature, to their recommended torque rating. It may be desirable to press the shims together with force while tightening the bolts. Also, the shims are aligned to provide uniform extrusion out the dispensing slot, as misalignment can lead to first and second segments extruding at an angle out of the die which may inhibit bonding between these segments. To aid in alignment, an indexing groove can be cut into the shims to receive a key. Also, a vibrating table can be useful to provide a smooth surface alignment of the extrusion tip.
The size of the various segments and layers in the film can be adjusted, for example, by the composition of the extruded polymers (e.g., materials, melt viscosities, additives, and molecular weight), pressure in the cavities, flow rate of the polymer stream, and/or the dimensions of the passageways.
In preparing the films described herein, the polymeric compositions might be solidified simply by cooling. This can be conveniently accomplished by, for example, quenching the extruded film or article on a chilled surface (e.g., a chilled roll). In some embodiments, it is desirable to maximize the time to quenching to increase the weld line strength.
The extrusion die useful for making a film such as that shown in
In many embodiments, there are multiple first slot segments and multiple second slot segments arranged along the width of the dispensing slot. In some of these embodiments, the first and second slot segments alternate such that one first slot segment is disposed between any two adjacent second slot segments. Similarly, one second slot segment can be disposed between any two adjacent first slot segments. It should be understood that for multiple first slot segments, each is fed by a first passageway that extends from the same first cavity. Likewise, for multiple second slot segments, each is fed by a second passageway that extends from the same second cavity and a third passageway that extends from the same die cavity within the extrusion die. Although the second slot segments allow for polymeric compositions, one from the second cavity and one from the die cavity to which the third fluid passageways are connected, to be layered in the thickness “z” direction, the second slot segments are not further divided in the width “x” direction. That is, multiple fluid passageways do not enter the second slot segments of the dispensing slot in a side-by-side arrangement. Accordingly, the layered second segments of the film extruded from the second slot segments are uniform in composition across their widths.
The combined width of the first and second slot segments should be understood to be the width of the first slot segment added to the width of the second slot segment. The width of the third fluid passageway at a point where it meets the second fluid passageway is less than the combined width of the first and second slot segments. The third fluid passageway is therefore generally distinguishable from a fluid passageway that extends across the width of the dispensing slot to provide, for example, a continuous skin layer of generally uniform composition on top of a side-by-side coextruded film. In some embodiments, the width of the third fluid passageway at a point where it meets the second fluid passageway is about the same as the width of the second slot segments.
A plurality of shims that is useful for providing a layered second segment in which layers on the first and second major surfaces are fed from the same cavity is shown in
Referring now to
Shim 1500 has several holes 1547 to allow the passage of, for example, bolts to hold shim 1500 and others to be described below into an assembly. Shim 1500 has dispensing opening 1556 in dispensing surface 1567. Dispensing opening 1556 may be more clearly seen in the expanded view shown in
Referring now to
Referring now to
Referring now to
Referring now to
Referring now to
Extrusion dies according to the present disclosure, which are useful for extruding the films disclosed herein, have a dispensing slot. The embodiment of
Referring now to
In this embodiment, inlet fittings 2250a, 2250b, and 2250c provide a flow path for three streams of molten polymer through end blocks 2244a and 2244b to cavities 1562a, 1562b, and 1562c. Compression blocks 2204 have a notch 2206 that conveniently engages the shoulders on the shims (e.g., 1590 and 1592 on 1500). When mount 2000 is completely assembled, compression blocks 2204 are attached by, e.g. machine bolts to backplates 2208. Holes are conveniently provided in the assembly for the insertion of cartridge heaters 52.
Referring now to
Another film that may be useful as an apertured film according to the present disclosure can have first segments and second segments each having first and second layers (e.g., with each layer in each of the first and second segments being of a different polymeric composition). Such a film can conveniently be extruded by the extrusion die shown in
Shim 3500 has several holes 3547 to allow the passage of, for example, bolts to hold shim 3500 and others to be described below into an assembly. Shim 3500 has dispensing opening 3556 in dispensing surface 3567. Dispensing opening 3556 may be more clearly seen in the expanded view shown in
Referring now to
Referring now to
Referring now to
Modifications of the shims shown in
The shims shown in
For more information regarding films including layered segments, see U.S. Pat. App. Pub. No. 2014/0248471 (Hanschen et al.), incorporated by reference herein in its entirety.
Dies useful for preparing film 600 as in the embodiment shown in
Referring now to
Shim 4540 has several holes 47 to allow the passage of, for example, bolts to hold shim 4540 and others to be described below into an assembly. Shim 4540 has dispensing opening 4566 in dispensing surface 4567. Dispensing opening 4566 may be more clearly seen in the expanded view shown in
Referring now to
Referring now to
Referring now to
Referring now to
Referring now to
The extrusion die described above in connection with
The extrusion die described above in connection with
For more information regarding films including stripes alternating with strands having a core and a sheath, see U.S. Pat. App. Pub. No. 2014/0093716 (Hanschen et al.), incorporated by reference herein in its entirety.
While each of
Films comprising alternating first and second segments useful for practicing the present disclosure include films wherein the first segments are made from a first polymeric composition, and wherein the second segments comprise strands of the elastic polymeric composition embedded in a matrix of the first polymeric composition that is continuous with the first segments. An example of these films is shown in
In some embodiments of the film or the method of making the film according to the present disclosure, the film may be stretched in at least one direction. When the film or extruded article disclosed herein is a web of indefinite length, for example, monoaxial stretching in the machine direction, which is typically the direction parallel to the longitudinal direction of the first and second segments, can be performed by propelling the web over rolls of increasing speed. Means such as diverging rails and diverging disks are useful for cross-direction stretching, which is typically the film width “x” direction. A versatile stretching method that allows for monoaxial, sequential biaxial, or simultaneous biaxial stretching of a thermoplastic web employs a flat film tenter apparatus. Such an apparatus grasps the thermoplastic web using a plurality of clips, grippers, or other film edge-grasping means along opposing edges of the thermoplastic web in such a way that monoaxial, sequential biaxial, or simultaneous biaxial stretching in the desired direction is obtained by propelling the grasping means at varying speeds along divergent rails. Increasing clip speed in the machine direction generally results in machine-direction stretching. Monoaxial and biaxial stretching can be accomplished, for example, by the methods and apparatus disclosed in U.S. Pat. No. 7,897,078 (Petersen et al.) and the references cited therein. Flat film tenter stretching apparatuses are commercially available, for example, from Brückner Maschinenbau GmbH, Siegsdorf, Germany. Other useful methods for stretching the films disclosed herein in one or more directions (e.g., “x” and “y” directions referring to
In some embodiments of the method of making the film according to the present disclosure, it is useful to stretch the film in one or more directions (e.g., “x” and “y” directions referring to
Films according to and/or made according to the present disclosure may have stretch-induced molecular orientation (e.g., in the first segments) after being stretched in at least one of the machine direction or cross-direction. Whether the first or second segments or other portions of the film have stretch-induced molecular orientation can be determined by standard spectrographic analysis of the birefringent properties of the oriented polymer forming the segments. The first or second segments or other portions of the film having stretch-induced molecular orientation may also be said to be birefringent, which means that the polymer in the oriented portion of the film has different effective indexes of refraction in different directions. In the present application, whether the first or second segments or other portions of the film have stretch-induced molecular orientation is measured with a retardance imaging system available from Lot-Oriel GmbH & Co., Darmstadt, Germany, under the trade designation “LC-PolScope” on a microscope available from Leica Microsystems GmbH, Wetzlar, Germany, under the trade designation “DMRXE” and a digital CCD color camera available from Qlmaging, Surrey, BC, Canada, under the trade designation “RETIGA EXi FAST 1394”. The microscope is equipped with a 546.5 nm interference filter obtained from Cambridge Research & Instrumentation, Inc., Hopkinton, Mass., and a 10×/0.25 objective. The degree of birefringence in an oriented film portion is typically observed to be higher in a film that has been stretched to the point of plastic deformation than in a film that only has melt-induced orientation in the machine direction. The difference in degree of birefringence between stretch-induced molecular orientation and melt-induced orientation would be understood by a person skilled in the art.
A variety of polymeric compositions are useful in any of the methods described above for making films comprising first and second segments. The mass flow (or volume flow) of the different polymeric compositions can be equal or unequal as they are respectively extruded. In some embodiments, it is desirable for the melt strengths of the different polymeric compositions to be similar. Polymeric compositions useful for the first and second segments (e.g., including core and sheath regions or various layers within the first and second segments) may be selected, for example, based on their compatibility and mutual adhesion properties.
In some embodiments, the polymeric compositions that may be extruded to make a film comprising first and second segments are thermoplastic polymeric compositions (e.g., polyolefins (e.g., polypropylene, polypropylene copolymers, polyethylene, and polyethylene copolymers), polyvinyl chloride, polystyrenes and polystyrene block copolymers, nylons, polyesters (e.g., polyethylene terephthalate), polyurethanes, polyacrylates, silicone polymers, and copolymers and blends thereof). However, polymeric materials that can be crosslinked (e.g., by heat or radiation) may also be useful for some embodiments. When a heat curable resin is used, a die described in any of the above methods can be heated to start the cure so as to adjust the viscosity of the polymeric material and/or the pressure in the corresponding die cavity.
The first segments in a film comprising alternating first and second segments are typically made from a first polymeric composition. The first polymeric composition can be relatively less elastic than the elastic polymeric composition in the second segments. The first polymeric composition can also be inelastic as defined above. The first polymeric composition can be formed, for example, of semicrystalline or amorphous polymers or blends. Inelastic polymers can be polyolefinic, formed predominantly of polymers such as polyethylene, polyethylene copolymers, polypropylene, polypropylene copolymers, polybutylene, or polyethylene-polypropylene copolymers. In some embodiments, the first polymeric composition comprises polypropylene, polyethylene, polypropylene-polyethylene copolymer, or blends thereof.
In the films comprising alternating first and second segments, second segments comprise an elastic polymeric composition that is more elastic than the first polymeric composition described above. Typically, the force required to stretch the second segments in the cross-machine direction is less than the force required to stretch the first segments. An elastic polymeric composition may be selected, for example, such that a film of the elastic polymeric composition (such as a film that is 0.002 mm to 0.5 mm thick) has an elongation of at least 200 percent at room temperature. Examples of useful elastic polymeric compositions include thermoplastic elastomers such as ABA block copolymers, polyurethane elastomers, polyolefin elastomers (e.g., metallocene polyolefin elastomers), olefin block copolymers, polyamide elastomers, ethylene vinyl acetate elastomers, and polyester elastomers. An ABA block copolymer elastomer generally is one where the A blocks are polystyrenic, and the B blocks are conjugated dienes (e.g., lower alkylene dienes). The A block is generally formed predominantly of substituted (e.g, alkylated) or unsubstituted styrenic moieties (e.g., polystyrene, poly(alphamethylstyrene), or poly(t-butylstyrene)), having an average molecular weight from about 4,000 to 50,000 grams per mole. The B block(s) is generally formed predominantly of conjugated dienes (e.g., isoprene, 1,3-butadiene, or ethylene-butylene monomers), which may be substituted or unsubstituted, and has an average molecular weight from about 5,000 to 500,000 grams per mole. The A and B blocks may be configured, for example, in linear, radial, or star configurations. An ABA block copolymer may contain multiple A and/or B blocks, which blocks may be made from the same or different monomers. A typical block copolymer is a linear ABA block copolymer, where the A blocks may be the same or different, or a block copolymer having more than three blocks, predominantly terminating with A blocks. Multi-block copolymers may contain, for example, a certain proportion of AB diblock copolymer, which tends to form a more tacky elastomeric film segment. Other elastic polymers can be blended with block copolymer elastomers, and various elastic polymers may be blended to have varying degrees of elastic properties.
The elastic polymeric composition can include many types of thermoplastic elastomers that are commercially available, including those from BASF, Florham Park, N.J., under the trade designation “STYROFLEX”, from Kraton Polymers, Houston, Tex., under the trade designation “KRATON”, from Dow Chemical, Midland, Mich., under the trade designation “PELLETHANE”, “INFUSE”, VERSIFY″, or “NORDEL”, from DSM, Heerlen, Netherlands, under the trade designation “ARNITEL”, from E. I. duPont de Nemours and Company, Wilmington, Del., under the trade designation “HYTREL”, from ExxonMobil, Irving, Tex. under the trade designation “VISTAMAXX”, and more.
The elastic polymeric composition can also include a blend of any of the elastomers described above and any of the polymers described above in the first polymeric composition. Similarly, the first polymeric composition may include a blend of relatively less elastic polymers and relatively more elastic polymers, as long as the elastic polymeric composition is more elastic than the first polymeric composition in the first segments. Generally, the first and elastic polymeric compositions should be selected so that the tensile modulus of the first segments is higher than the tensile modulus of the second segments. Less force will then be required to stretch the second segments, and as a result, the second segments will stretch first, allowing the apertures in the first segments to remain unstretched.
As described above, the first and elastic polymeric compositions can be selected based at least partially on their compatibility and mutual adhesion properties. Compatibility and adhesion between segments can be evaluated by a hang shear evaluation. The hang shear evaluation is carried out by hanging a 200-gram weight on a 2.54 cm long sample (measured in the longitudinal direction of the segments) having 3.8 cm exposed sample in the width direction. The evaluation is carried out at 100° F. (38° C.), and the time until the static load breaks the film is determined. The film is positioned so that the load is applied in the film width or cross-direction (that is, in a direction transverse to the longitudinal direction of the first and second segments). In some embodiments, the time to failure in a hang shear evaluation is at least 100 minutes, in some embodiments, at least 500 minutes, and in some embodiments, at least 1000 minutes. The time to failure in a hang shear evaluation may be influenced by a variety of factors. For example, for different first polymeric compositions, the elastic polymeric compositions that will provide the desired hang shear strength may be different. The presence of any plasticizers or compatibilizers may affect the hang shear strength. At least for these reasons, it is impractical to describe each composition that may provide a hang shear time of at least 100 minutes. A time to failure in a hang shear evaluation of at least 100 minutes (in some embodiments at least 500 or 1000 minutes) may be useful for evaluating, for example, films according to the present disclosure which are designed to be extended in the width or cross-direction of the film during use. However, lower time to failure may be useful in films, for example, which are designed to be extended in the longitudinal direction of the film after the film undergoes plastic deformation of relatively inelastic segments as described in further detail below.
For some embodiments, the first polymeric composition comprises polypropylene, and the elastic polymeric composition is selected such that it bonds well to polypropylene. In some of these embodiments, the elastic polymeric composition is a thermoplastic elastomer, for example, an ABA triblock copolymer elastomer or an ABAD tetrablock copolymer. In some embodiments, the elastic polymeric composition is an ABA triblock copolymer of styrene or substituted styrene as the A blocks and hydrogenated polybutadiene, hydrogenated polyisoprene, or a combination of hydrogenated polybutadiene and polyisoprene as the B block. The hydrogenated B block can therefore include polyethylene, polypropylene, and polybutylene moieties. Typically the time to failure in a hang shear evaluation of a film having second segments including such an elastic polymeric composition and first segments comprising polypropylene is at least 100 minutes (in some embodiments at least 500 or 1000 minutes). The polystyrene units in the ABA triblock copolymer may be present in a range from 20 to 60 percent or in a range from 25 to 45 percent by weight, based on the total weight of the ABA triblock copolymer. The hydrogenated conjugated diene units in the ABA triblock copolymer may be present in a range from 40 to 80 percent or in a range from 55 to 75 percent by weight, based on the total weight of the ABA triblock copolymer. The hydrogenated polyisoprene, when present, may be present in an amount up to 15, 10, or 5 percent by weight, based on the total weight of the ABA triblock copolymer. The weight average molecular weight of the ABA triblock copolymer may be in a range from 75,000 to 250,000 grams per mole, or 150,000 to 220,000 grams per mole. The number average molecular weight of the ABA triblock copolymer may be in a range from 50,000 to 200,000 grams per mole, or 120,000 to 200,000 grams per mole. Weight and number average molecular weights can be measured, for example, by gel permeation chromatography (i.e., size exclusion chromatography) using techniques known to one of skill in the art.
A third polymeric composition, which may be at one or both major surfaces of the second segments, may be the same as or different from the first polymeric composition. The third polymeric composition may be selected so that the elastic polymeric composition is also more elastic than the third polymeric composition. The third polymeric composition can be useful, for example, for protecting the elastic polymeric composition during manufacture or use and/or providing a less tacky surface on the elastic polymeric composition. If the third polymeric composition is selected such that it is softer than the first polymeric composition, the force required to initially stretch the film in the width “x” direction may be less than when the third polymeric compositions is a relatively more inelastic matrix.
In embodiments of the film or method disclosed herein that include a first polymeric composition, an elastic polymeric composition, and a third polymeric composition that is different from the first polymeric composition, blending may be useful for making a third polymeric composition that is relatively more elastic than the first polymeric composition but relatively less elastic than the elastic polymeric composition from which at least the first layers of the layered second segments are made. In some embodiments, the third polymeric composition comprises a blend of the first polymeric composition and the elastic polymeric composition. In these embodiments, the third polymeric composition generally has good compatibility with and good adhesion to both the first polymeric composition and the elastic polymeric composition. In some embodiments, the third polymeric composition may be a blend of an elastic resin and an inelastic resin but may not contain the resins in the first or elastic polymeric compositions.
In some embodiments, compatibilizers added to at least one of the second or third polymeric compositions may be useful. A compatibilizer may be useful, for example, for increasing the elongation of an elastic film, lowering the force required to stretch the film, and modifying the thicknesses of the second segments. Examples of suitable compatibilizers include hydrogenated cycloaliphatic resins, hydrogenated aromatic resins, and combinations thereof. For example, some compatibilizers are hydrogenated C9-type petroleum resins obtained by copolymerizing a C9 fraction produced by thermal decomposition of petroleum naphtha, hydrogenated C5-type petroleum resins obtained by copolymerizing a C5 fraction produced by thermal decomposition of petroleum naphtha, or hydrogenated C5/C9-type petroleum resins obtained by polymerizing a combination of a C5 fraction and C9 fraction produced by thermal decomposition of petroleum naphtha. The C9 fraction can include, for example, indene, vinyltoluene, alpha-methylstyrene, beta-methylstyrene, or a combination thereof. The C5 fraction can include, for example, pentane, isoprene, piperine, 1,3-pentadiene, or a combination thereof. Other compatibilizers include hydrogenated poly(cyclic olefin) polymers. Examples of hydrogenated poly(cyclic olefin) polymers include hydrogenated petroleum resins; hydrogenated terpene-based resins (for example, resins commercially available under the trade designation “CLEARON”, in grades P, M and K, from Yasuhara Chemical, Hiroshima, Japan); hydrogenated dicyclopentadiene-based resins (for example, those available from Kolon Industries, South Korea, under the trade designation “SUKOREZ”; a hydrogenated C5-type petroleum resin obtained by copolymerizing a C5 fraction such as pentene, isoprene, or piperine with 1,3-pentadiene produced through thermal decomposition of petroleum naphtha available, for example, from Exxon Chemical Co., Irving, Tex., under the trade designations “ESCOREZ 5300” or “ESCOREZ 5400”; and from Eastman Chemical Co., Kingsport, Tenn., under the trade designation “EASTOTAC H”); partially hydrogenated aromatic modified dicyclopentadiene-based resins commercially available, for example, from Exxon Chemical Co. under the trade designation “ESCOREZ 5600”; resins resulting from hydrogenation of a C9-type petroleum resin obtained by copolymerizing a C9 fraction such as indene, vinyltoluene and α- or β-methylstyrene produced by thermal decomposition of petroleum naphtha available, for example, from Arakawa Chemical Industries Co., Ltd. under the trade designations “ARCON P” or “ARCON M”; and resins resulting from hydrogenation of a copolymerized petroleum resin of the above-described C5 fraction and C9 fraction available, for example, from Idemitsu Petrochemical Co., Tokyo, Japan, under the trade designation “IMARV”. In some embodiments, the hydrogenated poly(cyclic olefin) is a hydrogenated poly(dicyclopentadiene). Other examples of useful compatibilizers can be found in U.S. Pat. No. 4,787,897 (Torimae et al.) and U.S. Pat. No. 6,669,887 (Hilston et al.). The compatibilizer is typically amorphous and has a weight average molecular weight up to 5000 grams per mole to preserve compatibility with the elastomeric resin. The molecular weight is often up to 4000 grams per mole, 2500 grams per mole, 2000 grams per mole, 1500 grams per mole, 1000 grams per mole, or up to 500 grams per mole. In some embodiments, the molecular weight is in the range of 200 to 5000 gram per mole, in the range of 200 to 4000 grams per mole, in the range of 200 to 2000 grams per mole, or in the range of 200 to 1000 gram per mole. When present, the compatibilizer may be in the second or third polymeric composition in a range from 15 percent to 30 percent by weight (in some embodiments, 15 to 25 percent by weight) based on the total weight of the second or third polymeric composition.
In some embodiments, polymeric materials used to make films useful for practicing the present disclosure may comprise a colorant (e.g., pigment and/or dye) for functional (e.g., optical effects) and/or aesthetic purposes (e.g., each has different color/shade). The pigment or die can also be useful as described above for absorbing light at a selected wavelength. Suitable colorants are those known in the art for use in various polymeric compositions. Examples of colors imparted by the colorant include white, black, red, pink, orange, yellow, green, aqua, purple, and blue. In some embodiments, it is desirable level to have a certain degree of opacity for one or more of the polymeric compositions. The amount of colorant(s) to be used in specific embodiments can be readily determined by those skilled in the art (e.g., to achieve desired color, tone, opacity, transmissivity, etc.).
In some embodiments, at least a portion of the film to be apertured according to the present disclosure include microvoids. In some embodiments, the first segments include microvoids. Microvoiding can be included in the film using a variety of methods. In some embodiments, microvoiding can be introduced into the first segments by beta-nucleation of semi-crystalline polyolefins. Certain heterogeneous nuclei, typically known as beta-nucleating agents, act as foreign bodies in a crystallizable polymer melt. When the polymer cools below its crystallization temperature (e.g., a temperature in a range from 60° C. to 120° C. or 90° C. to 120° C.), the loose coiled polymer chains orient themselves around the beta-nucleating agent to form beta-phase regions. The beta form of polypropylene is a meta-stable form, which can be converted to the more stable alpha form by thermal treatment and/or applying stress. Microvoids can be formed in various amounts when the beta-form of polypropylene is stretched under certain conditions; see, e.g., Chu et al., “Microvoid formation process during the plastic deformation of β-form polypropylene”, Polymer, Vol. 35, No. 16, pp. 3442-3448, 1994, and Chu et al., “Crystal transformation and micropore formation during uniaxial drawing of β-form polypropylene film”, Polymer, Vol. 36, No. 13, pp. 2523-2530, 1995. Typically the semi-crystalline polyolefin comprises polypropylene. It should be understood that a semi-crystalline polyolefin comprising polypropylene may be a polypropylene homopolymer or a copolymer containing propylene repeating units. The copolymer may be a copolymer of propylene and at least one other olefin (e.g., ethylene or an alpha-olefin having from 4 to 12 or 4 to 8 carbon atoms). Copolymers of ethylene, propylene and/or butylenes may be useful. In some embodiments, the copolymer contains up to 90, 80, 70, 60, or 50 percent by weight of polypropylene. In some embodiments, the copolymer contains up to 50, 40, 30, 20, or 10 percent by weight of at least one of polyethylene or an alpha-olefin. The semi-crystalline polyolefin may also be part of a blend of thermoplastic polymers that includes polypropylene. Suitable thermoplastic polymers include crystallizable polymers that are typically melt processable under conventional processing conditions. That is, on heating, they will typically soften and/or melt to permit processing in conventional equipment, such as an extruder, to form a sheet.
In some embodiments, the beta-nucleating agent is selected from the group consisting of gamma-quinacridone, a calcium salt of suberic acid, a calcium salt of pimelic acid and calcium and barium salts of polycarboxylic acids. In some embodiments, the beta-nucleating agent is quinacridone colorant Permanent Red E3B, which is also referred to as Q-dye. In some embodiments, the beta-nucleating agent is formed by mixing an organic dicarboxylic acid (e.g., pimelic acid, azelaic acid, o-phthalic acid, terephthalic acid, and isophthalic acid) and an oxide, hydroxide, or acid salt of a Group II metal (e.g., magnesium, calcium, strontium, and barium). So-called two component initiators include calcium carbonate combined with any of the organic dicarboxylic acids listed above and calcium stearate combined with pimelic acid. In some embodiments, the beta-nucleating agent is aromatic tri-carboxamide as described in U.S. Pat. No. 7,423,088 (Mader et al.). A convenient way of incorporating beta-nucleating agents into a semi-crystalline polyolefin useful for making a microporous film disclosed herein is through the use of a concentrate. The level of beta-spherulites in the semi-crystalline polyolefin can be determined, for example, using X-ray crystallography and Differential Scanning Calorimetry (DSC). By DSC, melting points and heats of fusion of both the alpha phase and the beta phase can be determined in a microporous film useful for practicing the present disclosure. For semi-crystalline polypropylene, the melting point of the beta phase is lower than the melting point of the alpha phase (e.g., by about 10 to 15 degrees Celsius). The ratio of the heat of fusion of the beta phase to the total heat of fusion provides a percentage of the beta-spherulites in a sample. The level of beta-spherulites can be at least 10, 20, 25, 30, 40, or 50 percent, based on the total amount of alpha and beta phase crystals in the film. These levels of beta-spherulites may be found in the film before it is stretched.
In some embodiments, the film useful for practicing the present disclosure in any of its embodiments is formed using a thermally induced phase separation (TIPS) method. This method of making the microvoided film typically includes melt blending a crystallizable polymer and a diluent (e.g., mineral oil, mineral spirits, dioctylphthalate, liquid paraffins, paraffin wax, glycerin, petroleum jelly, polyethylene oxide, polypropylene oxide, polytetramethylene oxide, soft carbowax, and combinations thereof) to form a melt mixture. The melt mixture is then formed into a film and cooled to a temperature at which the polymer crystallizes, and phase separation occurs between the polymer and diluent, forming voids. The voided film may have some degree of opacity. A nucleating agent may be useful in the first polymeric composition to facilitate crystallization. In some embodiments, the nucleating agent is a beta-nucleating agent described above. The quantity of diluent is typically in a range from about 20 parts to 70 parts, 30 parts to 70 parts, or 50 parts to 65 parts by weight, based upon the total weight of the polymer and diluent. In this manner a film is formed that comprises an aggregate of crystallized polymer in the diluent compound. Accordingly, in some embodiments, the first segments comprise a first polymeric composition comprising a polymer and a diluent that is miscible with the polymer at a temperature above a melting temperature of the polymer but that phase separates from the polymer at a temperature below a crystallization temperature of the polymer. The term “melting temperature” refers to the temperature at which the polymer in a blend that contains polymer and diluent will melt. The term “crystallization temperature” refers to the temperature at which the polymer in the blend will crystallize. The melting and crystallization temperature of a thermoplastic polymer, in the presence of a diluent and other additives, is influenced by both a phase equilibrium and a dynamic effect. At equilibrium between liquid and crystalline polymer phases, thermodynamics require that the chemical potentials of the polymer repeating unit in the two phases be equal. The temperature at which this condition is satisfied is referred to as the melting temperature, which will depend upon the composition of the melt mixture. The crystallization temperature and melting temperature are typically equivalent at equilibrium. However, at non-equilibrium conditions, which are normally the case, the crystallization temperature and melting temperature depend on the external cooling rate and heating rate, respectively. Consequently, the terms “melting temperature” and “crystallization temperature,” when used herein, are intended to include the equilibrium effect (i.e., the polymer/diluent system melts and crystallizes at the same temperature) as well as the dynamic effect of the rate of heating or cooling. The term “equilibrium melting point” refers to the commonly accepted melting temperature of the pure polymer, as may be available in published references.
In some embodiments, following formation of the crystallized polymer, the porosity of the material is increased by at least one of stretching the film in at least one direction or removing at least some of the diluent. This step results in a network of interconnected micropores. This step also permanently attenuates the polymer to form fibrils connecting the plurality of particles, imparting strength and porosity to the film. Pore sizes achieved from this method can range from about 0.2 micron to about 5 microns. The diluent can be removed from the material either before or after stretching. In some embodiments, the diluent is not removed. In some of these embodiments, the diluent can be useful as a plasticizer for the elastic polymeric composition in the second segments. The presence of the diluent may eliminate the need for other plasticizers in the elastic polymeric compositions, described below.
In some embodiments, the film useful for aperturing has microvoids formed using particulate cavitating agents. Such cavitating agents are incompatible or immiscible with the polymeric matrix material and form a dispersed phase within the polymeric core matrix material before extrusion and orientation of the film. When such a polymer substrate is subjected to uniaxial or biaxial stretching, a void or cavity forms around the distributed, dispersed-phase moieties, providing a film having a matrix filled with numerous cavities that provide an opaque appearance due to the scattering of light within the matrix and cavities. The particulate cavitating agents may be inorganic or organic. Organic cavitating agents generally have a melting point that is higher than the melting point of the film matrix material. Useful organic cavitating agents include polyesters (e.g., polybutylene teraphthalate or nylon such as nylon-6), polycarbonate, acrylic resins, and ethylene norbornene copolymers. Useful inorganic cavitating agents include talc, calcium carbonate, titanium dioxide, barium sulfate, glass beads, glass bubbles (that is, hollow glass spheres), ceramic beads, ceramic bubbles, and metal particulates. The particle size of cavitating agents is such that at least a majority by weight of the particles comprise an overall mean particle diameter, for example, of from about 0.1 micron to about 5 microns, in some embodiments, from about 0.2 micron to about 2 microns. (The term “overall” refers to size in three dimensions; the term “mean” is the average.) The cavitating agent may be present in the first polymeric composition, for example, in an amount of from about 2 weight percent to about 40 weight percent, about 4 weight percent to about 30 weight percent, or about 4 weight percent to about 20 weight percent, based upon the total weight of the polymer and cavitating agent. Some of these cavitating agents are also useful for absorbing light at the selected wavelength.
Films useful for practicing the present disclosure are typically extensible in the cross-machine direction (which is typically transverse to the direction of the longitudinally extending first and second segments), and less extensible in the machine direction. In some embodiments, the film disclosed herein has an elongation of at least 75 (in some embodiments, at least 100, 200, 250, or 300) percent and up to 1000 (in some embodiments, up to 750 or 500) percent). In some embodiments, films disclosed herein will sustain only small permanent set following deformation and relaxation (in some embodiments, less than 25, 20, or even less than 10 percent) of the original length after 100% elongation at room temperature.
In films according to the present disclosure and/or made according to the method of the present disclosure, the first and second segments each have a length, width, and height, wherein the length is the longest dimension and the thickness is the smallest dimension. In some embodiments, the width of each of the first and second segments is up to five millimeters. The width of the first and second segments is typically at least 100 micrometers (in some embodiments, at least 150 micrometers or 200 micrometers). In some embodiments, the widths of the second segments, which may include an elastic polymeric composition, in films disclosed herein are less than 1 millimeter (mm) (in some embodiments, up to 750 micrometers, 650 micrometers, 500 micrometers, or 400 micrometers). For example, the second segments may be in a range from 100 micrometers to less than 1 mm, 100 micrometers to 750 micrometers, 150 micrometers to 750 micrometers, 150 micrometers to 500 micrometers, or 200 micrometers to 600 micrometers wide.
In some embodiments, the films disclosed herein have first segments with widths up to 2 mm (in some embodiments, up to 1.5 mm, 1 mm or 750 micrometers). In some embodiments, the first segments are at least 100 micrometers, 150 micrometers, 250 micrometers, 350 micrometers, 400 micrometers, or 500 micrometers wide. For example, the first segments may be in a range from 250 micrometers to 1.5 mm, 100 micrometers to 1 mm, or 350 micrometers to 1 mm wide. As used herein, the width of the first and second segments is the dimension measured in the film's width direction “x”.
While the apparatus and method of making films disclosed herein are capable of extruding segments with widths up to 2 mm or 1 mm, such films could not practically be achieved by extrusion from apparatuses having continuous width flow channels up to 2 mm or 1 mm wide and at least 5 cm or 7.5 cm in length such as those described in Int. Pat. App. Pub. No. WO 2010/099148 (Hoium et al.). The pressure drop at the dispensing edge would limit the extrusion rates to less than 0.1 meters per minute, at least ten times slower than the extrusion rates achievable from the apparatus and method disclosed herein.
In some embodiments of the film disclosed herein, the distance between midpoints of two first segment separated by one second segment is up to 3 mm, 2.5 mm, or 2 mm. In some embodiments, the distance between midpoints of two first segments separated by one second segment is at least 300 micrometers, 350 micrometers, 400 micrometers, 450 micrometers, or 500 micrometers. In some embodiments, the distance between midpoints of two first segments separated by one second segment is in a range from 300 micrometers to 3 mm, 400 micrometers to 3 mm, 500 micrometers to 3 mm, 400 micrometers to 2.5 mm, or 400 micrometers to 2 mm.
The films disclosed herein in any of its embodiments may have a variety of useful thicknesses, depending on the desired use. In some embodiments, the film may be up to about 250 micrometers, 200 micrometers, 150 micrometers, or 100 micrometers thick. In some embodiments, the film may be at least about 10 micrometers, 25 micrometers, or 50 micrometers thick. For example, the thickness of the film may be in a range from 10 micrometers to 250 micrometers, from 10 micrometers to 150 micrometers, or from 25 micrometers to 100 micrometers thick. In some embodiments, the thickness of the first segments is within about 20%, 10%, or 5% of the thickness of the second segments. In these cases, the first segments may be said to have substantially the same thickness as the second segments. This may be useful, for example, for lowering the force to initially stretch the film, to maximize the elongation, and to lower the hysteresis of the film. In other embodiments, the thickness of the elastic segments may be at least 50%, 100%, 150%, or more higher than the first segments. This may be useful, for example, to provide a pleasing tactile ribbed texture to the film surface or to promote bonding predominantly to the elastic segments. The melt viscosities and/or die swells of the selected resins influence the thicknesses of the first and second segments. Resins may be selected for their melt viscosities, or, in some embodiments, a tackifier or other viscosity-reducing additive may be useful to decrease the melt viscosity of the resin, for example, a third polymeric composition used in a layer or sheath as described above. Die designs may also produce varying thicknesses of the film (e.g., by having a dispensing orifice that varies in size).
In first or second segments including layers or sheaths as described above, the second, third, fifth, and sixth layers described above in connection with
In some embodiments of the films disclosed herein, the density of the second segments, which may include a relatively more elastic polymeric composition, can vary across the web. This can be accomplished, for example, if sequences of shims in the die described herein include varying frequency of shim sequences providing the second segments. In some embodiments, it may be desirable to have a higher density of such second segments toward the center of the film. In other words, the distance between midpoints of successive first segments may or may not be identical. Measuring the distance between midpoints between successive first segments is convenient; however, distance could also be measured between any point of one first segment to a corresponding point in the next first segment of the film. In some embodiments, across a film there is an average of distances between midpoints of two first segments separated by one second segment, and for any two given first segments separated by one second segment, the distance is within 20 (in some embodiments, 15, 10, or 5) percent of the average of these distances across the film.
Measurements of the widths and/or thicknesses of first and second segments (e.g., including the first, second, and optionally third layers) or distances between two corresponding points on successive first or second segments may be made, for example, by optical microscopy. Optical microscopy is also useful to determine volume percentage of the first and second segments. In some embodiments, the first segments make up a higher volume percentage than the second segments. In some embodiments, the first segments make up a range of about 51% to 85% of the volume of the film, and the second segments make up a range of about 15% to 49% of the volume of the film. In some embodiments, the first segments make up a range of about 55% to 80% of the volume of the film, and the second segments make up a range of about 20% to 45% of the volume of the film.
Films according to and/or prepared using the method according to the present disclosure can be made with a variety of basis weights. For example, the basis weight of the film as extruded may be in a range from 15 grams per square meter to 100 grams per square meter. In some embodiments, the basis weight of the film is in a range from 20 grams per square meter to 60 grams per square meter. After the film is stretched, it may have a basis weight lower than 15 grams per square meter. It is useful that in these films, elastomeric polymers can make a relatively low contribution to the basis weight and yet useful elastic properties are achieved in the films and film articles. In some embodiments, the elastomeric polymers contribute up to 25, 20, 15, or 10 grams per square meter to the basis weight of the film. In some embodiments, elastomeric polymers contribute in a range from 3 to 10 grams per square meter to the basis weight of the film. The typically low amount of elastomeric polymer in the films and film articles described herein provides a cost advantage over elastic films in which elastomeric polymers make a higher contribution to the basis weight of the films.
In some embodiments of the films disclosed herein, the first segments, which contain the first polymeric composition that is relatively less elastic than the elastic polymeric composition, have molecular orientation resulting from stretching. In some of these embodiments, the first segments have stretch-induced molecular orientation in a width direction “x” caused by permanent plastic deformation. To achieve the permanent deformation, the film may be stretched to at least 500 (in some embodiments, at least 600 or 750) percent, depending on the elongation of the film. In these embodiments, the films disclosed herein can provide a “dead-stop” elastic film, in which the force required for extension rises rapidly during the last portion of extension.
In some embodiments, the films disclosed herein are stretched-activated in the longitudinal direction of the first and second segments. In some of these embodiments, the first segments have stretch-induced molecular orientation in a longitudinal direction “y” caused by permanent plastic deformation. To achieve the permanent deformation, the film may be stretched to at least 200 (in some embodiments, at least 300, 400, or 500) percent or more. When the elastic second segments relax after stretching, the stretched first segments are shined to form a textured surface. Such texture may eliminate the need for laminating the elastic film to a fibrous (e.g., nonwoven) carrier, especially if soft-feeling resins are used to make the film. Accordingly, in some embodiments, the film disclosed herein is not joined to a carrier. Furthermore, after stretching in the “y” direction, the films are remarkably strong in this direction. The process of stretching the relatively inelastic first segments in the machine direction can orient or tensilize those segments, offering strength and robustness during manufacturing line processing and in the end-use applications of the films.
In some embodiments where the film disclosed herein is not joined to a carrier, particles may be applied to one or both major surfaces of the film to provide a matte finish. In some embodiments, the film disclosed herein may be flocked with a fibrous material, such as any of those described below, to give the film a soft feeling without joining it to a carrier. In other embodiments, pattern-embossing the film on one or both major surfaces can provide an appearance or feeling of a fibrous material.
In laminates according to the present disclosure, the film disclosed herein is joined to a carrier. One or both major surfaces of the film may be joined to a carrier. The method disclosed herein further comprises joining a surface of the film to a carrier or joining both major surfaces of the film to a carrier. The carrier on opposite sides of the film may be the same or different. The film may be joined to a carrier, for example, by lamination (e.g., extrusion lamination), adhesives (e.g., hot melt or pressure sensitive adhesives), or other bonding methods (e.g., ultrasonic bonding, thermal bonding, compression bonding, or surface bonding). The film may be provided with apertures before, during, or after lamination.
The film and the carrier may be substantially continuously bonded or intermittently bonded. “Substantially continuously bonded” refers to being bonded without interruption in space or pattern. Substantially continuously bonded laminates can be formed by laminating a carrier to a substantially continuous film upon extrusion of the film; passing the film and the fibrous web between a heated smooth surfaced roll nip if at least one of them is thermally bondable; or applying a substantially continuous adhesive coating or spray to one of the film or carrier before bringing it in contact with the other of the film or carrier. “Intermittently bonded” can mean not continuously bonded and refers to the film and the carrier being bonded to one another at discrete spaced apart locations or being substantially unbonded to one another in discrete, spaced apart areas. Intermittently bonded laminates can be formed, for example, by passing the film and the carrier through a heated patterned embossing roll nip if at least one of them is heat bondable, or by applying discrete, spaced apart areas of adhesive to one of the film or the carrier before bringing it into contact with the other of the film or the carrier. An intermittently bonded laminate can also be made by feeding an adhesively coated aperture ply or scrim between the film and the carrier.
In some embodiments, the chemical compositions in the first and second segments differ at the surface of the film. The ability to select different compositions for the second and third layers or sheath of the second segments, for example, and the first segments offers the ability to bond selectively to either the first or second segments as desired. For example, a hot melt adhesive in at least one of the second and third layers in the second segments or fifth and sixth layers of the first segments can offer selective bonding to the desired segments. In some embodiments, the carrier is bonded predominantly to the first segments, which are relatively less elastic than the second segments. When a carrier is said to bond predominantly to either the first or second segments, it means that greater than 50, 60, 75, or 90 percent of the bonded area of the film is found in one of these locations but not in the other. Bonding predominantly to the first segments can be achieved, for example, through the selected materials for the first and second segments, through the geometry (e.g., height) of the first and second segments, or a combination of these. The first polymeric composition may be selected, for example, to have a similar chemical composition and/or molecular weight as the carrier to be bonded. Matching chemical composition and/or molecular weight for the bonding of two materials may be useful, for example, for thermal bonding, ultrasonic bonding, and compression bonding methods among others. An additive to the second or third layers in the second segments could be used to make it less receptive to bonding. For example, extrudable release materials, or lower surface energy materials than in the first segments, could be employed. In some embodiments, the first segments include fifth and sixth layers comprising a hot melt adhesive, and the second segments include second and third layers comprising a material that may be a non-adhesive or a material resistant to bonding (e.g., a soft polypropylene). The ability to preferentially bond to either the first or second segments using selection of materials may be more difficult in films, for example, in which multiple strands of one polymer are embedded within a continuous matrix of another polymer.
In laminates according to the present disclosure, the carrier may comprise a variety of suitable materials including woven webs, non-woven webs (e.g., spunbond webs, spunlaced webs, airlaid webs, meltblown web, and bonded carded webs), textiles, nets, and combinations thereof. In some embodiments, the carrier is a fibrous material (e.g., a woven, nonwoven, or knit material). The term “nonwoven” when referring to a carrier or web means having a structure of individual fibers or threads which are interlaid, but not in an identifiable manner as in a knitted fabric. Nonwoven fabrics or webs can be formed from various processes such as meltblowing processes, spunbonding processes, spunlacing processes, and bonded carded web processes. In some embodiments, the carrier comprises multiple layers of nonwoven materials with, for example, at least one layer of a meltblown nonwoven and at least one layer of a spunbonded nonwoven, or any other suitable combination of nonwoven materials. For example, the carrier may be a spunbond-meltbond-spunbond, spunbond-spunbond, or spunbond-spunbond-spunbond multilayer material. Or, the carrier may be a composite web comprising a nonwoven layer and a dense film layer.
Fibrous materials that provide useful carriers may be made of natural fibers (e.g., wood or cotton fibers), synthetic fibers (e.g., thermoplastic fibers), or a combination of natural and synthetic fibers. Exemplary materials for forming thermoplastic fibers include polyolefins (e.g., polyethylene, polypropylene, polybutylene, ethylene copolymers, propylene copolymers, butylene copolymers, and copolymers and blends of these polymers), polyesters, and polyamides. The fibers may also be multi-component fibers, for example, having a core of one thermoplastic material and a sheath of another thermoplastic material.
Useful carriers may have any suitable basis weight or thickness that is desired for a particular application. For a fibrous carrier, the basis weight may range, e.g., from at least about 5, 8, 10, 20, 30, or 40 grams per square meter, up to about 400, 200, or 100 grams per square meter. The carrier may be up to about 5 mm, about 2 mm, or about 1 mm in thickness and/or at least about 0.1, about 0.2, or about 0.5 mm in thickness. In some embodiments in which both major surfaces of the film are bonded to a fibrous carrier, it is sometimes advantageous if one fibrous carrier has a higher basis weight than the other.
Lamination of a film disclosed herein to one or more carriers may be carried out while the film is being stretched in its width “x” direction, while the film is being stretched in its longitudinal “y” direction, while the film is being stretched in both its width “x” and longitudinal “y” direction, or while not being stretched. Stretching the film may be carried out according to any of the methods described above. In some embodiments, machine direction stretching is carried out with differential speed rolls operating at increasingly greater speeds the further downweb they are located. Any number of two or more rolls may be useful. The speed may increase linearly or nonlinearly from one roll to the next. In other embodiments, differential speed rolls may deliver pulsed stretching. For example, a center roll may operate at a slower speed than rolls upweb and downweb, causing the film to go through sequences of stretch and recovery. The distance between adjacent rolls can be the same or different although the horizontal gap between rolls must be greater than the thickness of the film. The diameters of differential speed rolls can be the same or different. Upon stretching, lamination can be used to join one or two fibrous layers. Stretching films with side-by-side elastic and relatively inelastic segments beyond a point of plastic deformation just before lamination has several advantages. It is only when such films are stretched beyond the plastic deformation limit of the inelastic segments that the film can become elastic. As long as the tension on the films disclosed herein on a manufacturing line is below that required to exceed the deformation limit, the film is not likely to prematurely stretch on the manufacturing line. Also, the process of stretching the relatively inelastic first segments in the machine direction can orient or tensilize those segments, offering strength and robustness during manufacturing line processing and in the end-use applications of the laminates.
In some embodiments, including those embodiments described above that include stretching before lamination, laminates according to the present disclosure are prepared by ultrasonic bonding. Ultrasonic bonding generally refers to a process performed, for example, by passing layers between a sonic horn and a patterned roll (e.g., anvil roll). Such bonding methods are well-known in the art. For instance, ultrasonic bonding through the use of a stationary horn and a rotating patterned anvil roll is described in U.S. Pat. No. 3,844,869 (Rust Jr.) and U.S. Pat. No. 4,259,399 (Hill). Ultrasonic bonding through the use of a rotary horn with a rotating patterned anvil roll is described, for example, in U.S. Pat. No. 5,096,532 (Neuwirth, et al.); U.S. Pat. No. 5,110,403 (Ehlert); and U.S. Pat. No. 5,817,199 (Brennecke, et al.). Other ultrasonic bonding techniques may also be useful. In embodiments in which the film is stretched using differential speed rolls as described above, the patterned roll and furthest downweb differential speed roll may operate at the same speed. Or, in other embodiments, the patterned roll acts as an extension of the differential speed rolls, for example, and operate at an increased speed than the differential speed rolls. In some embodiments, a single fibrous carrier is laminated to the film. In embodiments in which the film has side-by-side elastic and relatively inelastic segments and has been stretched in the machine direction beyond the point of plastic deformation, an extensible laminate having a fibrous carrier on one side and the shined texture of the relaxed film on the other can be provided. The non-laminated surface can be non-tacky and soft to the touch if soft-feeling resins are used to make the film. In yet another embodiment, a single fibrous carrier is laminated to the films disclosed herein by any of the above-mentioned lamination processes where the films are colored, multi-colored and/or contain a print pattern. The films disclosed herein can be colored by the addition of pigments and/or dyes to one or more segments and layers. A print pattern can be added to the films disclosed herein using a variety of known printing processes.
In some embodiments of laminates disclosed herein, the film according to the present disclosure is joined to a fibrous web carrier using surface bonding or loft-retaining bonding techniques. The term “surface-bonded” when referring to the bonding of fibrous materials means that parts of fiber surfaces of at least portions of fibers are melt-bonded to a surface of the film in such a manner as to substantially preserve the original (pre-bonded) shape of the film surface, and to substantially preserve at least some portions of the film surface in an exposed condition, in the surface-bonded area. Quantitatively, surface-bonded fibers may be distinguished from embedded fibers in that at least about 65% of the surface area of the surface-bonded fiber is visible above the film surface in the bonded portion of the fiber. Inspection from more than one angle may be necessary to visualize the entirety of the surface area of the fiber. The term “loft-retaining bond” when referring to the bonding of fibrous materials means a bonded fibrous material comprises a loft that is at least 80% of the loft exhibited by the material prior to, or in the absence of, the bonding process. The loft of a fibrous material as used herein is the ratio of the total volume occupied by the web (including fibers as well as interstitial spaces of the material that are not occupied by fibers) to the volume occupied by the material of the fibers alone. If only a portion of a fibrous web has the film surface bonded thereto, the retained loft can be easily ascertained by comparing the loft of the fibrous web in the bonded area to that of the web in an unbonded area. It may be convenient in some circumstances to compare the loft of the bonded web to that of a sample of the same web before being bonded, for example, if the entirety of fibrous web has the film surface bonded thereto. In some of these embodiments, the joining comprises impinging heated gaseous fluid (e.g., ambient air, dehumidified air, nitrogen, an inert gas, or other gas mixture) onto a first surface of the fibrous web carrier while it is moving; impinging heated fluid onto the film surface while the continuous web is moving; and contacting the first surface of the fibrous web with the film surface so that the first surface of the fibrous web is melt-bonded (e.g., surface-bonded or bonded with a loft-retaining bond) to the film surface. Impinging heated gaseous fluid onto the first surface of the fibrous web and impinging heated gaseous fluid on the film surface may be carried out sequentially or simultaneously. Further methods and apparatus for joining a continuous web to a fibrous carrier web using heated gaseous fluid may be found in U.S. Pat. Appl. Pub. Nos. 2011/0151171 (Biegler et al.) and 2011/0147475 (Biegler et al.).
In some embodiments of the laminates according to the present disclosure, the carrier is a fibrous web activated by mechanical activation. Mechanical activation processes include stretching with diverging disks or incremental stretching methods such as ring-rolling, structural elastic film processing (SELFing), which may be differential or profiled, in which not all material is strained in the direction of stretching, and other means of incrementally stretching webs as known in the art. An example of a suitable mechanical activation process is the ring-rolling process, described in U.S. Pat. No. 5,366,782 (Curro). Specifically, a ring-rolling apparatus includes opposing rolls having intermeshing teeth that incrementally stretch and thereby plastically deform the fibrous web or a portion thereof forming the outer cover, thereby rendering the outer cover stretchable in the ring-rolled regions. Activation performed in a single direction (for example the cross direction) yields an outer cover that is uniaxially stretchable. Activation performed in two directions (for example the machine and cross directions or any two other directions maintaining symmetry around the outer cover centerline) yields an outer cover that is biaxially stretchable.
In some embodiments of the laminates according to the present disclosure, where the laminate includes a film disclosed herein in any of the aforementioned embodiments and an incrementally activated fibrous web, the distance between the midpoints between two first segments separated by one second segment is smaller than the pitch of the activation of the fibrous web. Activation pitch of the incrementally activated fibrous web is defined as the distance between the midpoints of two adjacent areas of higher deformation the fibrous web. Areas of higher deformation may be observed as areas of higher breakage, thinning, or higher elongation in the fibrous web. In some embodiments, areas of higher deformation may be observed as areas of a greater degree of shirring of the fibrous web. The activation pitch is typically equivalent to the pitch of the intermeshing surfaces in the apparatus used for incremental stretching. The pitch of the intermeshing surfaces is defined as the distance between two peaks of one of the intermeshing surfaces separated by one valley. The peaks can be defined as the apexes of outward pointing ridges of corrugated rolls (e.g., as described in U.S. Pat. No. 5,366,782 (Curro)) when such apparatuses are used. The peaks can also be defined as the peripheral surfaces (or center portion thereof) of discs used for incremental stretching such as those shown, for example, in U.S. Pat. No. 4,087,226 (Mercer). In other incremental stretching apparatuses, the peaks of one of the intermeshing surfaces would be readily identifiable to a person skilled in the art. In some embodiments of incrementally activated laminates according to the present disclosure, advantageously the first segments of the film, which include a first polymeric composition that is relatively less elastic than the elastic polymeric composition, are not plastically deformed in the laminate. Plastic deformation of the first segments can occur when the distance between the midpoints of two first segments separated by one second segment is larger than the activation pitch since the first segments can bridge between two peaks on one of the intermeshing surfaces. The plastically deformed regions can appear non-uniform resulting in a less aesthetically pleasing laminate, or the plastic deformation can result in breakage. In contrast, in embodiments of the laminate disclosed herein in which the distance between the midpoints between two first segments separated by one second segment is smaller than the pitch of the activation, the position and size of the first and second segments allow the second segments to stretch during incremental stretching of the laminate to take up the activation displacement without plastically deforming the first segments.
In some embodiments of the laminates according to the present disclosure, one or more zones of the carrier or the entire carrier may comprise one or more elastically extensible materials extending in at least one direction when a force is applied and returning to approximately their original dimension after the force is removed. In some embodiments, the extensible carrier is a nonwoven web that can be made by any of the nonwoven processes described above. The fibers for the nonwoven web may be made from elastic polymers, for example, any of those described above in connection with the second segments of the film disclosed herein. In some embodiments, the carrier may be extensible but inelastic. In other words, the carrier may have an elongation of at least 5, 10, 15, 20, 25, 30, 40, or 50 percent but may not recover to a large extent from the elongation (e.g., up to 40, 25, 20, 10 or 5 percent recovery). Suitable extensible carriers may include nonwovens (e.g., spunbond, spunbond meltblown spunbond, spunlace, or carded nonwovens). In some embodiments, the nonwoven may be a high elongation carded nonwoven (e.g., HEC). In some embodiments, the carrier may form pleats after it is extended. In some embodiments, the carrier is not pleated.
In some embodiments in which the laminate includes a fibrous web (e.g., a nonwoven web) that is extensible, a film or film article disclosed herein can be selected such that it has a relative low force to initially stretch the film. As described above, such a film can have, for example, second and optionally third layers in the second segments that are made from a softer, lower modulus material than the first segments and can have a geometry in which the thicknesses of the first and second segments are similar (e.g., within about 20%, 10%, or 5%). In these embodiments, the laminates may be considered not to require “activation”, and the ease of initially stretching the laminate would be apparent to the user.
Laminates of an extensible fibrous web and a film according to the present disclosure can advantageously be made by bonding under pressure discontinuously at discrete bond locations. The bonding can be carried out by a patterned embossing roll in which the pattern (that is, raised area) of the embossing roll provides up to about 30%, 25%, or 20% of the surface of the embossing roll. It is possible, but not required, that the pattern may be aligned with at least some of the first segments of the film. We have unexpectedly found that patterned bonding can be carried out in a nip at a temperature of up to 60° C., 55° C., 50° C., 40° C., 30° C., or even 25° C. using a pressure of at least one megapascal (MPa) (in some embodiments, 1.1, 1.2, 1.3, or 1.35 MPa).
If desired, lamination of the film according to the present disclosure to one or two fibrous carriers can be carried out such that certain zones are subjected to high heat and high pressure sufficient to create a non-stretchable zone in the laminate.
After laminates according to the present disclosure are prepared according to any of the methods described above, the laminate can be stored in roll form for incorporation into an article (e.g., those described below) in a separate process. In embodiments in which the film is stretched in at least one direction during lamination, the laminate can be stored in roll form in the stretched state and recovered at a later time. It is also possible to combine the method of making a laminate with a downline process of manufacturing an article. In embodiments in which the film is stretched in at least one direction during lamination, the laminate may be maintained in a stretched state and incorporated into an article in a downline process before allowing the web laminate to recover.
In some embodiments of the laminates disclosed herein, wherein the carrier is an elastic or extensible fibrous web, a tensile elongation at maximum load of the film is up to 250 percent of the tensile elongation at maximum load of the extensible fibrous web. In embodiments in which the film undergoes plastic deformation before breaking, the tensile elongation at maximum load of the film is the elongation at the point where the film begins to undergo plastic deformation. This extension is readily recognizable as a shoulder in a stress strain curve. In embodiments in which the film does not undergo plastic deformation before breaking, the tensile elongation at maximum load is the tensile elongation at break. The tensile elongation at maximum load of the fibrous web is generally the tensile elongation at break. In some embodiments, a tensile elongation at maximum load of the film is in a range from 25 percent to 250 percent, 50 percent to 225 percent, 75 percent to 200 percent, or 75 percent to 150 percent of the tensile elongation at maximum load of the extensible fibrous web. It is useful in laminates disclosed herein for the tensile elongation at maximum load of the film and the fibrous web to be comparable. In these laminates, there is not a large amount of unused elasticity in the film. For example, if an elastic film made completely of elastic polymers as described above has tensile elongation at maximum load of 800%, but an extensible fibrous web to which it is bonded only has a tensile elongation of about 200%, there is a large amount of elasticity in the film that is unused. Since more elastic polymers are typically more expensive than less elastic polymers, the unused elasticity translates to unnecessary expense. In the laminates according to the present disclosure, the first and second segments in the film allow for a lower amount of elastic polymers to be used while maintaining elongations that are comparable to extensible fibrous webs. On the other hand, the distribution of first and second segments across the film allow for more uniform extension than, for example, if only one segment of elasticity was used in the film. This distribution of first and second segments better utilizes the extensible potential of the extensible fibrous web. Furthermore, when the tensile elongation of the extensible fibrous web and the film are this similar, delamination of the extensible fibrous web and the film is less likely to occur than when, for example, the elastic film is much more extensible than the fibrous web.
In some embodiments of the laminates disclosed herein, a recoverable elongation of the laminate is at least 50% of the recoverable elongation of a comparative film after elongation of 100%. The laminate may be made from an extensible fibrous web, or the laminate may be incrementally activated as described above. The recoverable elongation can be understood to be the maximum elongation that provides the film or laminate with a permanent set of up to 20%, in some embodiments, up to 15% or 10%. The comparative film is the same as the film comprising first and second segments except that it is not laminated to a carrier. The comparative film may be a film that is removed from the laminate, for example, by submerging the laminate in liquid nitrogen and peeling apart the carrier and the film. Or the comparative film may be a sample made identically to the film comprising first and second segments but never laminated to a carrier. In some embodiments, a recoverable elongation of the laminate is at least 75%, 80%, 85%, 90% or 95% of the recoverable elongation of a comparative film at after elongation of 100%. Again, in any of these embodiments, there is not a large amount of unused elasticity in the elastic film. Also, in embodiments in which the carrier is an extensible fibrous web, the distribution of first and second segments better utilizes the recoverable elongation of the extensible fibrous web as described above. Also, where the comparative film is a sample made identically to the film comprising first and second segments but never laminated to an extensible fibrous web and subsequently incrementally stretched, when the recoverable elongation of the laminate is at least 50% (in some embodiments, 75%, 80%, 85%, 90%, or 95%) of the recoverable elongation of a comparative film after elongation of 100%, it is an indication that the incremental stretching did not plastically deform the first segments of the film.
Films disclosed herein have a variety of uses, including wound care and other medical applications (e.g., elastic bandage-like material, surface layer for surgical drapes and gowns, and cast padding), booties, tapes (including for medical applications), and absorbent articles (e.g., diapers, training pants, adult incontinence devices, and feminine hygiene products).
In absorbent articles, the film according to the present disclosure may be useful as a layer(s) within the articles and/or as part of an attachment system for the articles or elastic components. In some embodiments, a non-extensible region attached to the extensible region of the film can be used to attach the film article to the absorbent article or provide a fingerlift. In some embodiments, the non-extensible region can be formed with molded hooks to provide attachment to a loop. However, in some embodiments, the first segments or segments made from a relatively less elastic polymeric composition are not formed with male fastening elements (e.g., hooks) or upstanding posts or may not be formed with surface structure in general. Examples of disposable absorbent articles comprising films according to and/or made according to the present disclosure include disposable absorbent garments such as infant diapers or training pants, products for adult incontinence, and feminine hygiene products (e.g., sanitary napkins and panty liners). A typical disposable absorbent garment of this type is formed as a composite structure including an absorbent assembly (including, e.g., cellulosic fluff pulp, tissue layers, highly absorbent polymers (so called superabsorbents), absorbent foam materials, or absorbent nonwoven materials) disposed between a liquid permeable bodyside liner (e.g., nonwoven layers, porous foams, apertured plastic films) and a liquid impermeable outer cover (e.g., a thin plastic film, a nonwoven coated with a liquid impervious material, a hydrophobic nonwoven material which resists liquid penetration, or laminates of plastic films and nonwoven materials). These components can be combined with films disclosed herein and other materials and features such as further elastic components or containment structures to form the absorbent article.
In some embodiments, the film according to the present disclosure may be laminated to a fibrous (e.g., nonwoven) web. In some of these embodiments, the resulting laminate may be a fastening tab, for example, for an absorbent article. In some embodiments the resulting laminate may be an extensible ear, for example, for an absorbent article in some of these embodiments, the laminate may be in the shape of a trapezium.
In a first embodiment, the present disclosure provides a film comprising first and second segments arranged along the film's width direction, wherein the second segments are more elastic than the first segments, wherein the first segments absorb light at a selected wavelength to a greater extent than the second segments, wherein at least some of the first segments comprise apertures through their thicknesses, and wherein a percentage of area of the first segments occupied by the apertures is greater than a percentage of area occupied by any apertures that may extend through the second segments.
In a second embodiment, the present disclosure provides the film of the first embodiment, wherein the percentage of area of the first segments occupied by the apertures is at least 10 times greater than the percentage of area of the second segments occupied by apertures.
In a third embodiment, the present disclosure provides the film of the first or second embodiment, wherein the percentage of area of the second segments occupied by apertures is not more than one percent.
In a fourth embodiment, the present disclosure provides the film of any one of the first to third embodiments, wherein the second segments do not have apertures therethrough.
In a fifth embodiment, the present disclosure provides the film of any one of the first to fourth embodiments, wherein the first and second segments are alternating side-by-side stripes comprising a first polymeric composition and an elastic polymeric composition, respectively, wherein the elastic polymeric composition is more elastic than the first polymeric composition.
In a sixth embodiment, the present disclosure provides the film of any one of the first to fifth embodiments, wherein the film comprises a skin layer that extends over at least portions of both the first and second segments.
In a seventh embodiment, the present disclosure provides the film of any one of the first to fifth embodiments, wherein at least some of the first segments or second segments are layered segments comprising first and second layers in the film's thickness direction, and wherein the first and second layers have different polymeric compositions.
In an eighth embodiment, the present disclosure provides the film of any one of the first to fourth embodiments, wherein the first segments comprise a first polymeric composition, and wherein the second segments comprise strands of an elastic polymeric composition that is more elastic than the first polymeric composition embedded in a matrix of the first polymeric composition that is continuous with the first segments.
In a ninth embodiment, the present disclosure provides the film of any one of the first to fifth or seventh embodiments, wherein the first segments comprise a first polymeric composition, wherein the second segments are strands comprising a core and a sheath, wherein the core comprises an elastic composition and is more elastic than the sheath and more elastic than the first polymeric composition.
In a tenth embodiment, the present disclosure provides the film of any one of the first to ninth embodiments, wherein the second segments transmit the light at the selected wavelength.
In an eleventh embodiment, the present disclosure provides the film of any one of the first to ninth embodiments, wherein the second segments comprise an elastic polymeric composition that comprises an additive that reflects the light at the selected wavelength.
In a twelfth embodiment, the present disclosure provides the film of any one of the first to eleventh embodiments, wherein the first segments comprise a first polymeric composition that comprises an additive that causes the first polymeric composition to absorb ultraviolet light.
In a thirteenth embodiment, the present disclosure provides the film of the twelfth embodiment, wherein the first polymeric composition comprises at least one of titanium dioxide or calcium carbonate.
In a fourteenth embodiment, the present disclosure provides the film of any one of the first to eleventh embodiments, wherein the first segments comprise a first polymeric composition that comprises a dye that absorbs infrared light.
In a fifteenth embodiment, the present disclosure provides the film of any one of the first to fourteenth embodiments, wherein the first segments are plastically deformed.
In a sixteenth embodiment, the present disclosure provides the film of any one of the first to fifteenth embodiments, wherein the first segments further comprise microvoids.
In a seventeenth embodiment, the present disclosure provides the film of any one of the first to sixteenth embodiments, wherein when the film has a first moisture vapor transmission rate before stretching and a second moisture vapor transmission rate while stretching to 75% elongation, and wherein the second moisture vapor transmission rate is less than 50% greater than the first moisture vapor transmission rate.
In an eighteenth embodiment, the present disclosure provides the film of any one of the first to seventeenth embodiments, wherein the first segments make up a higher volume percentage of the film than the second segments.
In a nineteenth embodiment, the present disclosure provides the film of any one of the first to eighteenth embodiments, wherein the film has an elastic recovery of at least 40 percent.
In a twentieth embodiment, the present disclosure provides the film of any one of the first to nineteenth embodiments, wherein the first and second segments each have a length, width, and height, wherein the length is the longest dimension and the thickness is the smallest dimension, and width of each of the first and second segments is up to five millimeters.
In a twenty-first embodiment, the present disclosure provides a laminate comprising the film of any one of the first to twentieth embodiments joined to a fibrous carrier.
In a twenty-second embodiment, the present disclosure provides an absorbent article comprising the film of any one of the first to twentieth embodiments or the laminate of the twenty-first embodiment.
In a twenty-third embodiment, the present disclosure provides a method of making a film according to any one of the first to twentieth embodiments, the method comprising:
providing a film comprising first and second segments arranged along the film's width direction, wherein the second segments are more elastic than the first segments; and
forming apertures in at least some of the first segments using a laser at the selected wavelength, wherein the first segments have a sufficient absorbance of light at a selected wavelength to form apertures therethrough.
In a twenty-fourth embodiment, the present disclosure provides the method of the twenty-third embodiment, wherein the second segments have an insufficient absorbance at the selected wavelength to form apertures therethrough.
In a twenty-fifth embodiment, the present disclosure provides the method of the twenty-third or twenty-fourth embodiment, wherein the selected wavelength is in a range from 180 nanometers to one millimeter.
In a twenty-sixth embodiment, the present disclosure provides the method of any one of the twenty-third to twenty-fifth embodiments, wherein the laser is an ultraviolet laser, and wherein the selected wavelength is in a range from 180 nanometers to 355 nanometers.
In a twenty-seventh embodiment, the present disclosure provides the method of any one of the twenty-third to twenty-fifth embodiments, wherein the laser is a carbon dioxide laser, and wherein the selected wavelength is in a range from 9 micrometers to 11 micrometers.
In a twenty-eighth embodiment, the present disclosure provides the method of any one of the twenty-third to twenty-fifth embodiments, wherein the selected wavelength is in a range from 800 nanometers to one micrometer.
In a twenty-ninth embodiment, the present disclosure provides the method of any one of the twenty-third to twenty-eighth embodiments, further comprising laminating the film to a fibrous substrate before forming the apertures.
In a thirtieth embodiment, the present disclosure provides the method of any one of the twenty-third to twenty-ninth embodiments, wherein the film is part of a multilayer construction, and wherein the laser is focused the film within the multilayer construction.
In a thirty-first embodiment, the present disclosure provides the method of the thirtieth embodiment, wherein a fibrous layer is positioned between the laser and the film.
In a thirty-second embodiment, the present disclosure provides the method of any one of the twenty-third to thirty-first embodiments, further comprising stretching the film to plastically deform the first segments before forming the apertures.
In a thirty-third embodiment, the present disclosure provides the method of any one of the twenty-third to thirty-second embodiments, wherein forming the apertures comprises pulsing the laser.
In a thirty-fourth embodiment, the present disclosure provides the method of any one of the twenty-third to thirty-third embodiments, wherein the laser is not aligned with the first segments.
In a thirty-fifth embodiment, the present disclosure provides the method of any one of the twenty-third to thirty-fourth embodiments, wherein forming the apertures comprises exposing the film to the a laser pattern capable of exposing the second segments to the selected wavelength, but wherein the second segments have an insufficient absorbance at the selected wavelength to form apertures therethrough.
In any of the above embodiments, across at least a portion of the film's width the first and second segments can alternate.
In order that this disclosure can be more fully understood, the following examples are set forth. It should be understood that these examples are for illustrative purposes only, and are not to be construed as limiting this disclosure in any manner. All parts and percentages are by weight unless otherwise indicated.
The partially hydrogenated styrene triblock copolymer obtained under the trade designation “KRATON MD6843” used in some of the Examples, below, was analyzed by nuclear magnetic resonance (NMR) spectroscopy in solutions of unknown concentration in deuterated chloroform and deuterated 1,1,2,2-tetrachloroethane (TCE) using a 600 MHz NMR spectrometer obtained from Varian (Palo Alto, Calif.) under the trade designation “INOVA”. The spectrometer was equipped with a conventional room temperature inverse probe head. One-dimensional 1H-NMR and 13C-NMR spectra were collected followed by 1H/13C-NMR gradient heteronuclear single quantum coherence (gHSQC) and homo-nuclear two-dimensional NMR to confirm spectral assignments. The residual proto-solvent resonances were used as secondary chemical shift references in the proton dimension. All of the NMR data were collected with the samples held at 25° C. After analysis, it was concluded that hydrogenated butadiene moieties dominate the mid-block of the triblock copolymer, but minor amounts hydrogenated isoprene moieties were found in the mid-block as well. Integration of the 1H-NMR data suggested that polystyrene made up about 24 mole percent (36 weight percent) of the triblock copolymer.
The weight average and number average molecular weights of the partially hydrogenated styrene-butadiene-styrene copolymer obtained under the trade designation “KRATON MD6843” were determined by comparison to linear polystyrene polymer standards using gel permeation chromatography (GPC). The GPC measurements were carried out using a combined autosampler, controller and pump (Alliance Model 2695 Separations Module and Empower 3 data acquisition software obtained from Waters Corporation, Milford, Mass.) controlled to 40° C. and using three 250 millimeter (mm) by 10 mm linear columns of divinylbenzene polymer particles (obtained from Jordi Associates, Inc., Bellingham, Mass., under the trade designation “Jordi GEL”) with two columns of pore sizes Mixed Bed and one column of 500 angstroms. A differential refractive index (RI) detector (Waters Model 2414, obtained from Waters Corporation) was used at 40° C. A 20-milligram (mg) sample of the “MD6843” copolymer was diluted with 10 mL of tetrahydrofuran (inhibited with 250 ppm of BHT) into a 20-mL glass vial, capped with a polyethylene-lined cap and slowly rotated until dissolved. The sample solution was filtered through a 0.45-micrometer pore size 13-mm diameter polytetrafluoroethylene (PTFE) syringe filter into a 1.8-mL glass autosampler vial capped with a PTFE/silicone septum cap and placed in the autosampler along with two vials of polystyrene standards and a vial of control solution. At the beginning of the analysis, the tetrahydrofuran (inhibited with 250 ppm of BHT) mobile phase was incrementally brought to a flow rate of 1 mL/minute over six minutes, the reference side of the RI detector was flushed for 10 minutes and was filled with fresh tetrahydrofuran from the mobile phase. The sample was analyzed after 48 minutes of column equilibration, two 55-microliters injections of polystyrene standards and one 99-microliters injection of a control sample, each of 48 minutes duration. A sample volume of 99 microliters was injected onto the column bank and data collected by the Empower 3 software. Molecular weight calibration was performed using 15 narrow dispersity polystyrene standards (obtained from Polymer Standards Service-USA, Inc) with peak molecular weights ranging from 2.13×106 grams per mole to 266 grams per mole. The molecular weight distribution calculations were performed using Empower 3 GPC software using a third order polynomial fit and yielded an R value greater than 0.9995 for the molecular weight calibration curve. Duplicate injections were run and averaged. The weight average molecular weight of the triblock copolymer was found to be 181,600 grams per mole, and its number average molecular weight was found to be 159,000 grams per mole.
MVTR was measured using a stainless steel chamber containing calcium chloride. A sample of the film was placed over the top of the container, which had an opening having a radius of 30 mm, and threaded posts for accepting a rubber washer and stainless steel washer. A rubber washer and stainless steel washer each having three holes aligned with the posts were then sequentially placed over the film, and the assembly was tightening using wing nuts. The area of the exposed film was 0.002826 m2. The assembly was prepared in a room having a temperature of 20° C. and 50% humidity and weighed to provide the initial weight (W1). The assembly was then placed in an oven and heated at 50° C. and 75% humidity for five hours. The assembly was equilibrated for 30 minutes at 20° C. and 50% humidity and then weighed to provide the final weight (W2).
The MVTR in grams of water vapor transmitted per square meter (m2) of sample area per 24 hours was then calculated using the following formula:
MVTR=(W2−W1)g×(24 hours)/0.002826 m2×5 hours
When the MVTR was measured under tension, the method described above was repeated while the film was stretched to about 80% elongation and taped to the sides of the chamber.
A 6-inch (150-mm) co-extrusion die, Die 1, with three cavities, as generally depicted in
The inlet fittings on the two end blocks were each connected to conventional single-screw extruders. Compositions of the polymer compositions feeding each extruder and flow rates for each of Films 1 and 2 are shown in Table 2. Extruder 1 feeding the first cavity leading to the first fluid passageways described in Table 1, above, was loaded with the first polymeric composition. Extruder 2 fed the second cavity leading to the second fluid passageways, and Extruder 3 fed the third cavity leading to the third fluid passageways described in Table 1, above. Extruder 2 was loaded with the elastic polymeric composition, and Extruder 3 was loaded with the third polymeric composition. The first, elastic, and third polymeric compositions for each of Films 1 and 2 are shown in Table 2.
For Film 1, the first polymeric composition fed from Extruder 1 was a polypropylene impact copolymer obtained from Total Petrochemicals, Houston, Tex., under the trade designation “TOTAL POLYPROPYLENE 5571” that included 3% by weight of a titanium dioxide masterbatch obtained from Clariant, Minneapolis, Minn. The elastic polymeric composition fed from Extruder 2 was a mixture of 81% by weight of a styrene triblock copolymer with hydrogenated midblock obtained from Kraton Polymers, Houston, Tex., under the trade designation “KRATON MD6843” and 19% of a hydrogenated dicyclopentadiene hydrocarbon resin obtained from Kolon Industries, South Korea, under the trade designation “SUKOREZ SU-210”. The third polymeric composition fed from Extruder 3 was a mixture of a polypropylene random copolymer obtained from Total Petrochemicals under the trade designation “TOTAL POLYPROPYLENE 8650” that included about 2% by weight of a red color concentrate in polypropylene obtained from Clariant.
For Film 2, the first polymeric composition fed from Extruder 1 was a 50:50 blend of polypropylene impact copolymer obtained from Total Petrochemicals under the trade designation “TOTAL POLYPROPYLENE 5571” and a propylene based elastomer obtained from ExxonMobil, Houston, Tex., under the trade designation “VISTAMAXX 3980” that included 3% by weight of a titanium dioxide masterbatch obtained from Clariant. The elastic polymeric composition fed from Extruder 2 was a mixture of 75% by weight of a styrene triblock copolymer with hydrogenated midblock obtained from Kraton Polymers under the trade designation “KRATON MD6843” and 25% of a hydrogenated dicyclopentadiene hydrocarbon resin obtained from Kolon Industries under the trade designation “SUKOREZ SU-210”. The third polymeric composition fed from Extruder 3 was a mixture of a polypropylene random copolymer obtained from Total Petrochemicals under the trade designation “TOTAL POLYPROPYLENE 8650” that included about 3% by weight of a blue color concentrate in polypropylene obtained from Clariant.
All extruders were set to 218° C. The polymeric compositions were extruded from the die at a rate of 1.2 meters per minute (m/min) and then drawn at the rate shown in Table 2, below. A chill roll was positioned adjacent to the dispensing slot of the co-extrusion die to receive the extruded material.
A 100 cm by 200 cm area of Film 1 subjected to laser drilling. The sample was exposed to laser radiation at 355 nanometer wavelength from a 3-watt UV laser, “AVIA 355-3000” from Coherent Inc., Santa Clara, Calif. The laser energy was directed across the sample by a scanner Model HPLK 1330 from GSI Group, Billerica, Mass. The sample was positioned at a distance of approximately 300 mm from the scanner housing, which was in the focal plane of the scanner system. In the plane of the sample, the spot size for the laser beam was determined to be approximately 50 micrometers in width with a nearly Gaussian profile. The laser pattern was a point cloud array (5 mm by 5 mm) with each point given a drill duration of 4 to 50 milliseconds with a typical exposure of 5 milliseconds. The jump rate was 6 m/s with a trigger pulse of 4 microseconds. The laser was used at 70% of current to give approximately 40 millijoules per pulse. Apertures having an average diameter of about 100 micrometers spaced about 5 mm apart were formed in the first segments only.
Examples 2 and 3 were prepared using the method of Example 1 with the modification that for Example 2, a point cloud array 5 mm by 2.5 mm was used, and for Example 3, a cloud point array 5 mm by 1 mm was used. For Example 2, apertures having an average diameter of about 100 micrometers spaced about 2.5 mm apart were formed in the first segments only. For Example 3, apertures having an average diameter of about 100 micrometers spaced about 1 mm apart were formed in the first segments only.
A photomicrograph for a film prepared as described in Example 3 is shown in
Moisture vapor transmission rate was measured for Examples 1 to 3 using the test method described above. The MVTR was measured for the film when it was in a relaxed state and when it was stretched to about 80% elongation and held under tension. The percent difference between the MVTR in the relaxed state and under tension was calculated. The results are shown in Table 3, below.
Example 4 was prepared using the method of Example 1 with the modification that a point cloud array of 0.8 mm by 0.8 mm was used, and the laser beam was pulsed for 1 millisecond at a frequency of approximately 10 kHz, providing about ten pulses per hole. Apertures having an average diameter of about 50 micrometers spaced about 0.8 mm apart were formed in the first segments only.
Example 5 was prepared using the method of Example 4 except that Film 2 was used instead of Film 1.
A 100 cm by 200 cm area of Film 1 subjected to laser drilling. The sample was exposed to laser radiation at 10.6 micron wavelength from a CO2 laser, E-400 from Coherent, Inc. The laser energy was directed across the sample by the Model HPLK 1330 scanner. The sample was positioned at a distance of approximately 600 mm from the scanner housing (whereas the focal plane of the scanner system was located at approximately 560 mm from the scanner housing). In the plane of the sample, the spot size for the laser beam was determined to be approximately 220 micrometers in width with a nearly Gaussian profile. A column of points spaced from 0.5 mm to 15 mm was set with the laser set to drill mode.
For Illustrative Example 1, a paper overlay was placed over the sample, and the laser beam was used at 10% of Current (40 Watts) at a Galvo speed of approximately 4 m/sec. This resulted in apertures in both the first segments and second segments with a spacing between apertures of about 4.4 mm.
For Illustrative Example 2, the laser was used at 4% of current (10 Watts), and the target film was aligned manually and indexed for each of the first segments to produce the row of apertures in the first segments only. The spacing between apertures in the first segments was 4.4 mm. Three apertures were measured and found to have diameters of 0.202 mm, 0.192 mm, and 0.186 mm. The width of the first segment was measured to be 1.994 mm, and the width of the elastic lanes was measured at 0.729 mm and 0.717 mm. When the sample was stretched to 82% elongation, three apertures were measured and found to have diameters of 0.191 mm, 0.206 mm, and 0.206 mm. The width of the first segment was measured to be 2.028 mm, and the width of the elastic lanes was measured at 2.908 mm and 2.953 mm.
For Illustrative Example 3, the laser was used at 5% of current (20 Watts), and the target film was aligned manually and indexed for each of the first segments to produce the row of apertures in the first segments only. The spacing between apertures in the first segments was 4.4 mm. Three apertures were measured and found to have areas about 3 times larger than those of Illustrative Example 2.
Moisture vapor transmission rate was measured for Illustrative Examples 1 to 3 (Ill. Ex. 1 to 3) using the test method described above. The MVTR was measured for the film when it was in a relaxed state and when it was stretched to approximately 80% elongation and held under tension. The percent difference between the MVTR in the relaxed state and under tension was calculated. The results are shown in Table 4, below.
Foreseeable modifications and alterations of this disclosure will be apparent to those skilled in the art without departing from the scope and spirit of this invention. This invention should not be restricted to the embodiments that are set forth in this application for illustrative purposes.
This application claims priority to U.S. Provisional Application Nos. 62/032,246, filed Aug. 1, 2014; 61/974,877, filed Apr. 3, 2014; and 61/974,870, filed Apr. 3, 2014; the disclosures of which are incorporated by reference in their entirety herein.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2015/024285 | 4/3/2015 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 61974870 | Apr 2014 | US | |
| 61974877 | Apr 2014 | US | |
| 62032246 | Aug 2014 | US |
