NONWOVEN FABRICS COMPRISING POLYLACTIC ACID HAVING IMPROVED STRENGTH AND TOUGHNESS

- Fitesa Germany GmbH

Nonwoven fabrics having a plurality of fibers that are bonded to each other to form a coherent web, wherein the fibers comprise a blend of a polylactic acid (PLA) and at least one secondary alkane sulfonate are provided. The nonwoven fabrics exhibit increased tensile strengths, elongation and toughness.

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Description
CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of U.S. Provisional Application No. 62/375,648, filed Aug. 16, 2016, and the benefit of U.S. patent application Ser. No. 15/676,163, filed Aug. 14, 2017, and U.S. patent application Ser. No. 17/574,768, filed Jan. 13, 2022, the entire contents of all which are hereby incorporated by reference.

FIELD

The presently-disclosed invention relates generally to nonwoven fabrics, and more particularly to nonwoven fabrics comprising polylactic acid (PLA).

BACKGROUND

Nonwoven fabrics are used in a variety of applications such as garments, disposable medical products, diapers, personal hygiene products, among others. New products being developed for these applications have demanding performance requirements, including comfort, conformability to the body, freedom of body movement, good softness and drape, adequate tensile strength and durability, and resistance to surface abrasion, pilling or fuzzing. Accordingly, the nonwoven fabrics which are used in these types of products must be engineered to meet these performance requirements.

Traditionally, such nonwoven fabrics are prepared from thermoplastic polymers, such as polyester, polystyrene, polyethylene, and polypropylene. These polymers are generally very stable and can remain in the environment for a long time. Recently, however, there has been a trend to develop articles and products that are considered environmentally friendly and sustainable. As part of this trend, there has been a desire to produce ecologically friendly products comprised of increased sustainable content in order to reduce the content of petroleum based materials.

Polylactic acid or polylactide-based polymers (PLA) provide a cost-effective path to sustainable content spunbond nonwovens that can be readily converted into consumer products. To fully capture the cost-effective benefits of PLA-based consumer products, PLA must be convertible into nonwovens and then into the final consumer product at very high speeds with minimal waste. However, due to the propensity of static generation and accumulation on fibers with PLA polymer on the surface, it is difficult to combine the steps of spinning, web formation, and bonding at the very high speeds needed for the economically attractive production of spunbond PLA with optimum fabric properties.

To address this need, nonwovens have been developed having a sheath/core bicomponent structure in which the PLA is present in the core, and a synthetic polymer, such as polypropylene, is in the sheath. An example of such a nonwoven fabric is described in U.S. Pat. No. 6,506,873. The presence of the synthetic polymer in the sheath provides the necessary properties for commercial production of nonwovens comprising PLA at high speeds. Although commercial production of nonwovens comprising PLA with synthetic polymers in the sheath is possible, the industry (and its consumers) are seeking nonwovens having PLA on the surface of the fabric by either having PLA in the sheath or being 100% PLA.

Accordingly, there still exists a need for fabrics having PLA that exhibit improved mechanical properties.

SUMMARY

One or more embodiments of the invention may address one or more of the aforementioned problems. Certain embodiments according to the invention provide polylactic acid (PLA) spunbond nonwoven fabrics, sustainable composites including said fabrics, and sustainable articles including said fabrics and/or composites. In particular, embodiments of the invention are directed to fabrics, composites, and articles comprising PLA.

Certain embodiments according to the invention are directed to a spunbond nonwoven fabric comprising a plurality of fibers that are bonded to each other to form a coherent web, wherein the fibers comprise a blend of a polylactic acid (PLA) and at least one secondary alkane sulfonate. In some embodiments, the blend is present at a surface of the plurality of fibers.

In one embodiment, the at least one secondary alkane sulfonate comprises an alkane chain having from C10-C18, and wherein at least one of the secondary carbons of the alkane chain includes a sulfonate moiety. For example, the at least one secondary alkane sulfonate has one of the following structures:

wherein m+n is a number between 7 and 16, and X is independently a C1-C4 alkyl or absent. In some embodiments, the at least one secondary alkane sulfonate has the following structure:

wherein m+n is a number between 8 and 15, and in particular, wherein m+n is a number between 11 and 14. In some embodiments, the at least one secondary alkane sulfonate comprises a salt of sodium or potassium.

In certain embodiments, the at least one secondary alkane sulfonate is present in an amount ranging from about 0.0125 to 2.5 weight percent, based on the total weight of the fiber. For example, the fiber may have a sheath/core bicomponent arrangement in which the blend is present in the sheath, and wherein the secondary alkane sulfonate is present in the sheath in an amount ranging from about 0.1 to 0.75 weight percent, based on the total weight of the sheath. In another embodiment, the fiber may have a sheath/core bicomponent arrangement in which the blend is present in the sheath, and wherein the secondary alkane sulfonate is present in the sheath in an amount ranging from about 0.2 to 0.6 weight percent, based on the total weight of the sheath. In yet another embodiment, the fiber has a sheath/core bicomponent arrangement in which the blend is present in the sheath, and wherein the secondary alkane sulfonate is present in the sheath in an amount ranging from about 0.3 to 0.4 weight percent, based on the total weight of the sheath.

In one embodiment, the plurality of fibers comprise bicomponent fibers. In some embodiments, the plurality of fibers comprise bicomponent fibers and the at least one secondary alkane sulfonate is present in only one of the component of the fibers. In one embodiment, the bicomponent fibers have a sheath/core configuration and the sheath comprises a blend of the PLA and the at least one secondary alkane sulfonate. In some embodiments, the core comprises PLA and does not include the at least one secondary alkane sulfonate. In still other embodiments, the bicomponent fibers comprise a side-by-side arrangement.

In one embodiment, the core comprises at least one of a polyolefin, a polyester, a PLA, or any combination thereof. In a preferred embodiment, each of the sheath and the core comprises PLA. In certain embodiments, the sheath comprises a first PLA grade, the core comprises a second PLA grade, and the first PLA grade and the second PLA grade are different.

Surprisingly, the inventors have discovered that the addition of the secondary alkane sulfonate to the PLA resin improves the mechanical properties of the fabric. In particular, the fabric may exhibit an increase in tensile strength, elongation and toughness in at least one of the machine direction or cross direction in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate. For example, the fabric may exhibit an increase in tensile strength in at least one of the machine direction or cross direction of at least 50% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In yet another aspect, embodiments of the invention are directed to a spunbond nonwoven fabric comprising a plurality of fibers that are bonded to each other to form a coherent web, wherein the fibers comprise from 95 to 100% polylactic acid (PLA), and wherein the fibers exhibit a root mean square of a Toughness Index per basis weight having a value that is at least 55 N/m2. In one embodiment, the fabric has a root mean square of the Toughness Index per basis weight is a value that is greater than 65 N-%/g/m2, such as a value that is greater than 85 N-%/g/m2. In a preferred embodiment, the fabric has a root mean square of the Toughness Index per basis weight is a value from about from about 65 to 150 N-%/g/m2. Preferably, the fabric comprises fibers having less than 5 weight % of additives, and more preferably less than 4 weight %, based on the total weight of the fabric.

Additional aspects of the invention are directed to articles comprising the nonwoven fabric and to a process and system for preparing the fabric.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)

Having thus described the invention in general terms, reference will now be made to the accompanying drawings, which are not necessarily drawn to scale, and wherein:

FIGS. 1A and 1B are SEM images of individual bond points on a surface of a nonwoven fabric that does not include a secondary alkane sulfonate;

FIGS. 2A and 2B are SEM images of individual bond points on a surface of a nonwoven fabric that includes a secondary alkane sulfonate;

FIG. 3 is a schematic diagram of the PLA spunbond nonwoven fabric preparation system in accordance with certain embodiments of the invention;

FIGS. 4A-4C are schematic diagrams illustrating positioning of the first ionization source in accordance with certain embodiments of the invention;

FIGS. 5A-5D are cross-sectional views of composites in accordance with certain embodiments of the invention;

FIG. 6A is an illustration of an absorbent article in accordance with at least one embodiment of the invention;

FIG. 6B is a cross-sectional view of the absorbent article of FIG. 6A taken along line 72-72 of FIG. 6A; and

FIG. 7 is an illustration of an absorbent article in accordance with at least one embodiment of the invention in which the absorbent article is in the form of a feminine sanitary pad.

 DETAILED DESCRIPTION

The invention now will be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the inventions are shown. Indeed, this inventions may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements. Like numbers refer to like elements throughout. As used in the specification, and in the appended claims, the singular forms “a”, “an”, “the”, include plural referents unless the context clearly dictates otherwise.

The invention includes, according to certain embodiments, polylactic acid (PLA) spunbond nonwoven fabrics, sustainable composites including said fabrics, and absorbent articles including said fabrics and/or composites. In particular, embodiments of the invention are directed to fabrics, composites, and articles in which PLA is present on the fabric surface.

PLA spunbond nonwoven fabrics and sustainable composites including said fabrics may be used in a wide variety of applications, including diapers, feminine care products, wiper products, incontinence products, agricultural products (e.g., root wraps, seed bags, crop covers and/or the like), industrial products (e.g., work wear coveralls, airline pillows, automobile trunk liners, sound proofing articles and/or the like), and household products (e.g., furniture scratch pads, mattress coil covers and/or the like).

I. Definitions

For the purposes of the present application, the following terms shall have the following meanings:

The term “fiber” can refer to a fiber of finite length or a filament of infinite length.

As used herein, the term “monocomponent” refers to fibers formed from one polymer or formed from a single blend of polymers. Of course, this does not exclude fibers to which additives have been added for color, anti-static properties, lubrication, hydrophilicity, liquid repellency, etc.

As used herein, the term “multicomponent” refers to fibers formed from at least two polymers (e.g., bicomponent fibers) that are extruded from separate extruders. The at least two polymers can each independently be the same or different from each other, or be a blend of polymers. The polymers are arranged in substantially constantly positioned distinct zones across the cross-section of the fibers. The components may be arranged in any desired configuration, such as sheath-core, side-by-side, pie, island-in-the-sea, and so forth. Various methods for forming multicomponent fibers are described in U.S. Pat. No. 4,789,592 to Taniguchi et al. and U.S. Pat. No. 5,336,552 to Strack et al., U.S. Pat. No. 5,108,820 to Kaneko, et al., U.S. Pat. No. 4,795,668 to Kruege, et al., U.S. Pat. No. 5,382,400 to Pike, et al., U.S. Pat. No. 5,336,552 to Strack, et al., and U.S. Pat. No. 6,200,669 to Marmon, et al., which are incorporated herein in their entirety by reference. Multicomponent fibers having various irregular shapes may also be formed, such as described in U.S. Pat. No. 5,277,976 to Hogle, et al., U.S. Pat. No. 5,162,074 to Hills, U.S. Pat. No. 5,466,410 to Hills, U.S. Pat. No. 5,069,970 to Largman, et al., and U.S. Pat. No. 5,057,368 to Largman, et al., which are incorporated herein in their entirety by reference.

As used herein, the terms “nonwoven,” “nonwoven web” and “nonwoven fabric” refer to a structure or a web of material which has been formed without use of weaving or knitting processes to produce a structure of individual fibers or threads which are intermeshed, but not in an identifiable, repeating manner. Nonwoven webs have been, in the past, formed by a variety of conventional processes such as, for example, meltblown processes, spunbond processes, and staple fiber carding processes.

As used herein, the term “meltblown” refers to a process in which fibers are formed by extruding a molten thermoplastic material through a plurality of fine, usually circular, die capillaries into a high velocity gas (e.g. air) stream which attenuates the molten thermoplastic material and forms fibers, which can be to microfiber diameter. Thereafter, the meltblown fibers are carried by the gas stream and are deposited on a collecting surface to form a web of random meltblown fibers. Such a process is disclosed, for example, in U.S. Pat. No. 3,849,241 to Buntin et al.

As used herein, the term “machine direction” or “MD” refers to the direction of travel of the nonwoven web during manufacturing.

As used herein, the term “cross direction” or “CD” refers to a direction that is perpendicular to the machine direction and extends laterally across the width of the nonwoven web.

As used herein, the term “spunbond” refers to a process involving extruding a molten thermoplastic material as filaments from a plurality of fine, usually circular, capillaries of a spinneret, with the filaments then being attenuated and drawn mechanically or pneumatically. The filaments are deposited on a collecting surface to form a web of randomly arranged substantially continuous filaments which can thereafter be bonded together to form a coherent nonwoven fabric. The production of spunbond non-woven webs is illustrated in patents such as, for example, U.S. Pat. Nos. 3,338,992; 3,692,613, 3,802,817; 4,405,297 and 5,665,300. In general, these spunbond processes include extruding the filaments from a spinneret, quenching the filaments with a flow of air to hasten the solidification of the molten filaments, attenuating the filaments by applying a draw tension, either by pneumatically entraining the filaments in an air stream or mechanically by wrapping them around mechanical draw rolls, depositing the drawn filaments onto a foraminous collection surface to form a web, and bonding the web of loose filaments into a nonwoven fabric. The bonding can be any thermal or chemical bonding treatment, with thermal point bonding being typical.

As used herein, the term “thermal point bonding” involves passing a material such as one or more webs of fibers to be bonded between a heated calender roll and an anvil roll. The calender roll is typically patterned so that the fabric is bonded in discrete point bond sites rather than being bonded across its entire surface.

As used herein, the term “polymer” generally includes, but is not limited to, homopolymers, copolymers, such as, for example, block, graft, random and alternating copolymers, terpolymers, etc. and blends and modifications thereof. Furthermore, unless otherwise specifically limited, the term “polymer” shall include all possible geometrical configurations of the material, including isotactic, syndiotactic and random symmetries.

The term “composite”, as used herein, may be a structure comprising two or more layers, such as a film layer and a fiber layer or a plurality of fiber layers molded together. The two layers of a composite structure may be joined together such that a substantial portion of their common X-Y plane interface, according to certain embodiments of the invention.

Embodiments of the invention are directed to nonwoven fabrics comprising polylactic acid that exhibit improvements in strengths and toughness. In one embodiment, the present invention provides a spunbond nonwoven fabric comprising a plurality of fibers that are bonded to each other to form a coherent web, and wherein the plurality fibers comprise a blend of a PLA resin and at least one secondary alkane sulfonate. As explained in greater detail below, the inclusion of a secondary alkane sulfonate in the PLA resin improves the strength and toughness of the fabric in comparison to an identical fabric that does not include the secondary alkane sulfonate.

The at least one secondary alkane sulfonate typically comprises an alkane chain having from C10-C18, and wherein at least one of the secondary carbons of the alkane chain includes a sulfonate moiety. In particular, the at least one secondary alkane sulfonate may comprise a sulfonic acid, C13-C17-secondary alkane, sodium salt.

The alkane chain is generally linear although some chains may include some minor branching (e.g., C1-C4 side chain branching). Typically, the alkane chain will have from 10 to 18 carbon atoms, with an alkane chain length of 14 to 17 carbon atoms being somewhat more preferred. The secondary alkane sulfonate may include both mono- and disulfonic acids. However, the amount of monosulfonic acids in the secondary alkane sulfonate may generally be greater than 90%.

In one embodiment, the at least one secondary alkane sulfonate has one of the following structures:

wherein m+n is a number between 7 and 16, and X is independently a C1-C4 alkyl or absent. In a preferred embodiment, the secondary alkane sulfonate has the following structure:

wherein m+n is a number between 8 and 15, and more preferably m+n is a number between 11 and 14. The secondary alkane sulfonate typically comprises a salt of sodium or potassium, but other cations could be used, such as a salt of calcium or magnesium. Alternatively, a quaternary ammonium comprised of modified fatty alkyl substrates such as those based on coco or stearyl substrates could be used. Such quaternary amines are available from Air Products and Chemicals, Inc. of Allentown, PA 18195-1501, USA.

In one embodiment, the secondary alkane sulfonate may be provided in a masterbatch carrier resin. For example, in one embodiment, the secondary alkane sulfonate is provided in a PLA polymer carrier resin that is blended with the PLA prior to spinning of the fibers. Typically, the amount of secondary alkane sulfonate in the PLA masterbatch is from about 5 to 25 weight percent based on the total weight of the masterbatch, with an amount from 10 to 20 weight percent being somewhat more typical. The masterbatch may also include additional additives, such as one or more compatibilizers. A commercial example of a secondary alkane sulfonate that may be used in embodiments of the claimed invention includes SUKANO*under the product name S546-Q1, which is a C14-C17 secondary alkane sulfonate sodium salt in a PLA masterbatch. One skilled in the art would recognize that design of a masterbatch for a secondary alkane sulfonate is a compromise between maximizing the use of PLA resins with very similar melt flow as observed for the base resin of the fiber, such as, for example, NatureWorks 6202D or 6252 D (Melt Index g/10 minutes (210° C.) 15-30 or 15, respectively, and the ease of suspending the secondary alkane sulfonate in a PLA polymer. Thus, a suitable masterbatch may be comprised of a PLA grade such as Nature Works 6362D with a higher melt Index (Melt Index g/10 minutes (210° C.) of 70-85.

A wide variety of different PLA resins may be used to prepare nonwoven fabrics in accordance with embodiments of the invention. Generally, polylactic acid based polymers are prepared from dextrose, a source of sugar, derived from field corn. In North America corn is used since it is the most economical source of plant starch for ultimate conversion to sugar. However, it should be recognized that dextrose can be derived from sources other than corn. Sugar is converted to lactic acid or a lactic acid derivative via fermentation through the use of microorganisms. Lactic acid may then be polymerized to form PLA. In addition to corn, other agricultural based sugar sources may be used including rice, sugar beets, sugar cane, wheat, cellulosic materials, such as xylose recovered from wood pulping, and the like.

The PLA resin should have proper molecular properties to be spun in spunbond processes. Examples of suitable include PLA resins are supplied from NatureWorks LLC, of Minnetonka, MN 55345 such as, grade 6752D, 6100D, and 6202D, which are believed to be produced as generally following the teaching of U.S. Pat. Nos. 5,525,706 and 6,807,973 both to Gruber et al. Other examples of suitable PLA resins may include L130, L175, and LX175, all from Corbion of Arkelsedijk 46, 4206 A C Gorinchem, the Netherlands.

In some embodiments, the nonwoven fabrics may be biodegradable. “Biodegradable” refers to a material or product which degrades or decomposes under environmental conditions that include the action of microrganisms. Thus, a material is considered as biodegradable if a specified reduction of tensile strength and/or of peak elongation of the material or other critical physical or mechanical property is observed after exposure to a defined biological environment for a defined time. Depending on the defined biological conditions, a fabric comprised of PLA might or might not be considered biodegradable.

A special class of biodegradable products made with a bio-based material might be considered as compostable if it can be degraded in a composing environment. The European standard EN 13432, “Proof of Compostability of Plastic Products” may be used to determine if a fabric or film comprised of sustainable content could be classified as compostable.

In some embodiments, the PLA nonwoven fabrics may comprise sustainable polymer components of biodegradable products that are derived from an aliphatic component possessing one carboxylic acid group (or a polyester forming derivative thereof, such as an ester group) and one hydroxyl group (or a polyester forming derivative thereof, such as an ether group) or may be derived from a combination of an aliphatic component possessing two carboxylic acid groups (or a polyester forming derivative thereof, such as an ester group) with an aliphatic component possessing two hydroxyl groups (or a polyester forming derivative thereof, such as an ether group).

The term “aliphatic polyester” covers—besides polyesters which are made from aliphatic and/or cycloaliphatic components exclusively also polyesters which contain besides aliphatic and/or cylcoaliphatic units aromatic units, as long as the polyester has substantial sustainable content.

In addition to PLA based resins, nonwoven fabrics in accordance with embodiments of the invention may include other polymers derived from an aliphatic component possessing one carboxylic acid group and one hydroxyl group, which are alternatively called polyhydroxyalkanoates (PHA). Examples thereof are polyhydroxybutyrate (PHB), poly-(hydroxybutyrate-co-hydroxyvaleterate) (PHBV), poly-(hydroxybutyrate-co-polyhydroxyhexanoate) (PHBH), polyglycolic acid (PGA), poly-(epsilon-caprolactione) (PCL) and preferably polylactic acid (PLA).

Examples of additional polymers that may be used in embodiments of the invention include polymers derived from a combination of an aliphatic component possessing two carboxylic acid groups with an aliphatic component possessing two hydroxyl groups, and are polyesters derived from aliphatic diols and from aliphatic dicarboxylic acids, such as polybutylene succinate (PBSU), polyethylene succinate (PESU), polybutylene adipate (PBA), polyethylene adipate (PEA), polytetramethylene adipate/terephthalate (PTMAT).

Nonwoven fabrics in accordance with the invention may comprise monocomponent, bicomponent, or multicomponent fibers. Examples of bicomponent fibers include side-by-side, islands in the sea, and sheath/core arrangements. Preferably, the fibers have a sheath/core structure in which the sheath comprises a first polymer component, and the core comprises a second polymer component. In this arrangement, the polymers of the first and second polymer components may be the same or different from each other.

In a preferred embodiment, the fibers of the nonwoven fabric have a bicomponent arrangement in which the PLA blend comprising the secondary alkane sulfonate comprises a first polymer component defining a sheath, and a second polymer component comprises the core. Advantageously, the inventors have discovered that by blending the secondary alkane sulfonate into the polymer component defining the sheath, nonwoven fabrics having improved strength and toughness are provided. In addition, such improvements in physical properties may be obtainable in the absence of blending the secondary alkane sulfonate into the polymer component defining the core, which may help reduce the overall costs of preparing the nonwoven fabric.

In preferred embodiments, the sheath and the core both comprise a PLA resin. In these embodiments, a PLA spunbond nonwoven fabric may be provided that is substantially free of synthetic polymer components, such as petroleum-based materials and polymers. For example, the fibers of the PLA spunbond nonwoven fabric may have a bicomponent arrangement in which the both components are PLA based to thus produce a fiber that is 100% PLA.

As used herein, “100% PLA” may also include up to 5% additives including additives and/or masterbatches of additives to provide, by way of example only, color, softness, slip, antistatic protection, lubricity, hydrophilicity, liquid repellency, antioxidant protection and the like. In this regard, the nonwoven fabric may comprise 95-100% PLA, such as from 96-100% PLA, 97-100% PLA, 98-100% PLA, 99-100% PLA, etc. When such additives are added as a masterbatch, for instance, the masterbatch carrier may primarily comprise PLA in order to facilitate processing and to maximize sustainable content within the fibers.

For example, the PLA spunbond nonwoven fabric layer may comprise one or more additional additives. In such embodiments, for instance, the additive may comprise at least one of a colorant, a softening agent, a slip agent, an antistatic agent, a lubricant, a hydrophilic agent, a liquid repellent, an antioxidant, and the like, or any combination thereof.

In one embodiment, the PLA polymer of the sheath may be the same PLA polymer as that of the core. In other embodiments, the PLA polymer of the sheath may be a different PLA polymer than that of the core. For example, the bicomponent fibers may comprise PLA/PLA reverse bicomponent fibers such that the sheath comprises a first PLA grade, the core comprises a second PLA grade, and the first PLA grade and the second PLA grade are different (e.g., the first PLA grade has a higher melting point than the second PLA grade). By way of example only, the first PLA grade may comprise up to about 5% crystallinity, and the second PLA grade may comprise from about 40% to about 50% crystallinity.

In other embodiments, for instance, the first PLA grade may comprise a melting point from about 125° C. to about 135° C., and the second PLA grade may comprise a melting point from about 155° C. to about 170° C. In further embodiments, for example, the first PLA grade may comprise a weight percent of D isomer from about 4 wt. % to about 10 wt. %, and the second PLA grade may comprise a weight percent of D isomer of about 2 wt. %.

For example, in one embodiment, the core may comprise a PLA having a lower % D isomer of polylactic acid than that of the % D isomer PLA polymer used in the sheath. The PLA polymer with lower % D isomer will show higher degree of stress induced crystallization during spinning while the PLA polymer with higher D % isomer will retain a more amorphous state during spinning. The more amorphous sheath will promote bonding while the core showing a higher degree of crystallization will provide strength to the fiber and thus to the final bonded web. In one particular embodiment, the Nature Works PLA Grade PLA 6752 with 4% D Isomer can be used as the sheath while NatureWorks Grade 6202 with 2% D Isomer can be used as the core.

Generally, the weight percentage of the sheath to that of the core in the fibers may vary widely depending upon the desired properties of the nonwoven fabric. For example the weight ratio of the sheath to the core may vary between about 10:90 to 90:10, and in particular from about 20:80 to 80:20. In a preferred embodiment, the weight ratio of the sheath to the core is about 25:75 to 35:65, with a weight ratio of about 30:70 being preferred.

In other embodiments, a nonwoven fabric comprising bicomponent fibers is provided in which one of the polymer components comprises a blend of a PLA polymer and the secondary alkane sulfonate, and the other polymer component comprises a synthetic polymer, such as a petroleum derived polymer. Examples of synthetic polymers that may be used in embodiments of the invention may include polyolefins, such as polypropylene and polyethylene, polyesters, such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), and polybutylene terephthalate (PBT), nylons, polystyrenes, copolymers, and blends thereof, and other synthetic polymers that may be used in the preparation of fibers.

The amount of the secondary alkane sulfonate in the fibers will generally depend on where the secondary alkane sulfonate is present in the structure of the fibers, and the final desired properties of the nonwoven fabric. In general, the amount of the secondary alkane sulfonate may range from about 0.0125 weight percent to about 2.5 weight percent, based on the total weight of the polymeric component of the fiber in which the secondary alkane sulfonate is present. For example, in monocomponent fibers the weight percent of the secondary alkane sulfonate in the fibers will be based on the total weight of the fiber. In such a case, the amount secondary alkane sulfonate may range from about 0.0125 weight percent to about 2.5 weight percent, based on the total weight of the fiber. However, in the case of a bicomponent fiber, the weight percent of the secondary alkane sulfonate will be based on the total weight of the component in which the secondary alkane sulfonate is present. For example, in the case of a bicomponent fiber having a sheath to core weight ratio of 30:70, and in which the secondary alkane sulfonate is only present in the sheath, the weight percent of the secondary alkane sulfonate in the fiber may range from about 0.0125 weight percent to about 2.5 weight percent, based on the total weight of the sheath, which results in a weight percent of the secondary alkane sulfonate that is from 0.00375 to 0.750, based on the total weight of the fiber.

In one embodiment, the amount of the secondary alkane sulfonate may be at least about any one of the following: at least 0.0125, at least 0.0250, at least 0.0375, at least 0.050, at least 0.0625, at least 0.075, at least 0.100, at least 0.125, at least 0.150, at least 0.1875, at least 0.2, at least 0.2475, at least 0.25, at least 0.3 at least 0.375, at least 0.40, at least 0.495, at least 0.50, at least 0.60, at least 0.80, at least 0.9904, at least 1.0, at least 1.25, at least 1.2375, at least 1.5, at least 1.875, at least 2.0, and at least 2.50, based on the total weight of the polymeric component of the fiber in which the secondary alkane sulfonate is present. In other embodiments, the amount of the secondary alkane sulfonate may be less than about any one of the following: 0.0250, 0.0375, 0.050, 0.0625, 0.075, 0.100, 0.125, 0.150, 0.1875, 0.2, 0.2475, 0.25, 0.3, 0.375, 0.40, 0.495, 0.50, 0.60, 0.80, 0.9904, 1.0, 1.25, 1.2375, 1.5, 1.875, 2.0, and 2.50 weight percent. It should also be recognized that the amount of the secondary alkane sulfonate present in a polymer component of the fiber also encompasses ranges between the aforementioned amounts.

In a preferred embodiment, the fibers have a bicomponent structure in which the core and sheath both comprise a PLA polymer, and the sheath includes the secondary alkane sulfonate that is present in an amount that is from about 0.1 to 1 weight percent, based on the total weight of the sheath component, and in particular, from about 0.1 to 0.75, and more particularly from about 0.2 to 0.6 weight percent, and even more particularly, from about 0.3 to 0.4 weight percent, based on the total weight of the sheath component. Although, the secondary alkane sulfonate has generally discussed as being present in a monocomponent fiber or the sheath of a bicomponent fiber, it should be recognized that other arrangements are within the embodiments of the present invention. For example, the secondary alkane sulfonate may be present in only the core and not the sheath of a bicomponent fiber, or the secondary alkane sulfonate may be present in both the sheath and the core.

As the amount of the secondary alkane sulfonate in the fibers may vary depending on the amount of the secondary alkane sulfonate in the masterbatch polymer, the structure of the fiber (e.g., monocomponent or bicomponent), and in the case of the bicomponent, the ratio of a first polymer component to a second component in the fiber, the following tables provide exemplary ranges of the secondary alkane sulfonate in various fiber structures and at various loadings of the secondary alkane sulfonate in the masterbatch polymer, and at various loadings of the masterbatch in the PLA polymer.

TABLE 1A Amounts of the Secondary Alkane Sulfonate (SAS) in the Sheath of a bicomponent fiber having a sheath to core weight ratio of 50:50 at various SAS and Master Batch (MB) loadings Amount Amount Amount Amount of SAS in of SAS in of SAS in of SAS in Sheath at Sheath at Sheath at Sheath at Amount an addition an addition an addition an addition of SAS of 5% MB of 10% MB of 20% MB of 25% MB in MB to Sheath to Sheath to Sheath to Sheath (%) polymer (%) polymer (%) polymer (%) polymer (%) 0.25% 0.0125 0.025 0.050 0.0625 0.50% 0.025 0.050 0.100 0.125 0.75% 0.0375 0.075 0.150 0.1875  1.0% 0.050 0.100 0.200 0.250  2.0% 0.100 0.200 0.400 0.500  3.0% 0.150 0.300 0.600 0.750  4.0% 0.200 0.400 0.800 1.000 4.95% 0.2475 0.495 0.9904 1.2375  5.0% 0.250 0.500 1.00 1.2500  7.5% 0.375 0.750 1.500 1.8750 10.0% 0.500 1.000 2.000 2.5000

TABLE 1B Amounts of the Secondary Alkane Sulfonate (SAS) in the Fabric comprised of bicomponent fibers having a sheath to core weight ratio of 50:50 at various SAS and Master Batch (MB) loadings Amount Amount Amount Amount of SAS in of SAS in of SAS in of SAS in Fabric at Fabric at Fabric at Fabric at Amount an addition an addition an addition an addition of SAS of 5% MB of 10% MB of 20% MB of 25% MB in MB to Sheath to Sheath to Sheath to Sheath (%) polymer (%) polymer (%) polymer (%) polymer (%) 0.25% 0.00625 0.0125 0.025 0.03125 0.50% 0.01250 0.025 0.050 0.06250 0.75% 0.01875 0.0375 0.075 0.09375  1.0% 0.02500 0.050 0.100 0.12500  2.0% 0.05000 0.100 0.200 0.25000  3.0% 0.07500 0.150 0.300 0.37600  4.0% 0.10000 0.200 0.400 0.50000 4.95% 0.12375 0.2475 0.495 0.61875  5.0% 0.12500 0.250 0.500 0.62500  7.5% 0.18750 0.375 0.750 0.93750 10.0% 0.25000 0.500 1.000 1.25000

TABLE 2A Amounts of the Secondary Alkane Sulfonate (SAS) in Sheath of a bicomponent fiber having a sheath to core weight ratio of 30:70 at various SAS and Master Batch (MB) loadings Amount Amount Amount Amount of SAS in of SAS in of SAS in of SAS in Sheath at Sheath at Sheath at Sheath at Amount an addition an addition an addition an addition of SAS of 5% MB of 10% MB of 20% MB of 25% MB in MB to Sheath to Sheath to Sheath to Sheath (%) polymer (%) polymer (%) polymer (%) polymer (%) 0.25% 0.0125 0.025 0.050 0.0625 0.50% 0.025 0.050 0.100 0.125 0.75% 0.0375 0.075 0.150 0.1875  1.0% 0.050 0.100 0.200 0.250  2.0% 0.100 0.200 0.400 0.500  3.0% 0.150 0.300 0.600 0.750  4.0% 0.200 0.400 0.800 1.000 4.95% 0.2475 0.495 0.9904 1.2375  5.0% 0.250 0.500 1.00 1.2500  7.5% 0.375 0.750 1.500 1.8750 10.0% 0.500 1.000 2.000 2.5000

TABLE 2B Amounts of the Secondary Alkane Sulfonate (SAS) in the Fabric comprised of bicomponent fibers having a sheath to core weight ratio of 30:70 at various SAS and Master Batch (MB) loadings Amount Amount Amount Amount of SAS in of SAS in of SAS in of SAS in Fabric at Fabric at Fabric at Fabric at Amount an addition an addition an addition an addition of SAS of 5% MB of 10% MB of 20% MB of 25% MB in MB to Sheath to Sheath to Sheath to Sheath (%) polymer (%) polymer (%) polymer (%) polymer (%) 0.25% 0.00375 0.0075 0.015 0.01875 0.50% 0.00750 0.0150 0.0300 0.0375 0.75% 0.01125 0.0225 0.04500 0.05625  1.0% 0.0150 0.0300 0.0600 0.0750  2.0% 0.030 0.060 0.1200 0.1500  3.0% 0.0450 0.0900 0.1800 0.2250  4.0% 0.0600 0.1200 0.2400 0.3000 4.95% 0.07425 0.1485 0.2970 0.37125  5.0% 0.0750 0.1500 0.3000 0.375  7.5% 0.1125 0.2250 0.4500 0.5625 10.0% 0.1500 0.3000 0.6000 0.7500

TABLE 3 Amounts of the Secondary Alkane Sulfonate (SAS) in a Fabric comprising PLA monocomponent fibers at various SAS and Master Batch (MB) loadings Amount Amount Amount Amount Amount of SAS in of SAS in of SAS in of SAS in of SAS Fabric at an Fabric at an Fabric at an Fabric at an in MB addition of addition of addition of addition of (%) 5% MB (%) 10% MB (%) 20% MB (%) 25% MB (%) 0.25% 0.0125 0.025 0.050 0.0625 0.50% 0.025 0.050 0.100 0.125 0.75% 0.0375 0.075 0.150 0.1875  1.0% 0.050 0.100 0.200 0.250  2.0% 0.100 0.200 0.400 0.500  3.0% 0.150 0.300 0.600 0.750  4.0% 0.200 0.400 0.800 1.000 4.95% 0.2475 0.495 0.9904 1.2375  5.0% 0.250 0.500 1.600 1.25  7.5% 0.375 0.750 1.500 1.875 10.0% 0.500 1.000 2.000 2.500

In accordance with certain embodiments, for example, the nonwoven fabric may have a basis weight from about 7 grams per square meter (gsm) to about 150 gsm. In other embodiments, for instance, the fabric may have a basis weight from about 8 gsm to about 70 gsm. In certain embodiments, for example, the fabric may comprise a basis weight from about 10 gsm to about 50 gsm. In further embodiments, for instance, the fabric may have a basis weight from about 11 gsm to about 30 gsm. As such, in certain embodiments, the fabric may have a basis weight from at least about any of the following: 7, 8, 9, 10, and 11 gsm and/or at most about 150, 100, 70, 60, 50, 40, and 30 gsm (e.g., about 9-60 gsm, about 11-40 gsm, etc.).

Moreover, fabrics prepared in accordance with embodiments of the invention may be characterized by an area shrinkage of less than 5%. In further embodiments, for example, the fabrics may be characterized by an area shrinkage of less than 2%.

According to certain embodiments, for example, the fibers may have a linear mass density from about 1 dtex to about 5 dtex. In other embodiments, for instance, the fibers may have a dtex from about 1.5 dtex to about 3 dtex. In further embodiments, for example, the fibers may have a linear mass density from about 1.6 dtex to about 2.5 dtex. As such, in certain embodiments, the fibers have a linear mass density from at least about any of the following: 1, 1.1, 1.2, 1.3, 1.4, 1.5, and 1.6 dtex and/or at most about 5, 4.5, 4, 3.5, 3, and 2.5 dtex (e.g., about 1.4-4.5 dtex, about 1.6-3 dtex, etc.).

Advantageously, the inventors of the present invention have discovered that the addition of the secondary alkane sulfonate in the PLA resin provides significant increases in mechanical properties in comparison to an identical or similarly prepared nonwoven fabric that does not include the secondary alkane sulfonate. In this regard, nonwoven fabrics in accordance with embodiments of the present invention may exhibit tensile strengths that are 50% greater in comparison to a similarly prepared nonwoven fabric that does not include the secondary alkane sulfonate. In some embodiments, the nonwoven fabric may exhibit a tensile strength that is from 50% to 200% greater than the tensile strength of a similarly prepared nonwoven fabric that does not include the secondary alkane sulfonate.

In particular, nonwoven fabrics in accordance with the present invention may exhibit increases in machine direction (MD) tensile strengths that are from about 55 to 125% in comparison to a similarly prepared nonwoven fabric that does not include the secondary alkane sulfonate. In some embodiments, the inventive nonwoven fabrics may exhibit an increase in MD tensile strength ranging from about 50 to 150%, such as from about 55 to 125%, from about 65 to 110%, from about 85 to 110%, or from about 90 to 110%, in comparison to a similarly prepared nonwoven fabric that does not include the secondary alkane sulfonate.

In some embodiments, nonwoven fabrics in accordance with the present invention may exhibit increases in cross direction (CD) tensile strengths that are from about 50 to 200% in comparison to a similarly prepared nonwoven fabric that does not include the secondary alkane sulfonate. In some embodiments, the inventive nonwoven fabrics may exhibit an increase in CD tensile strength ranging from about 50 to 170%, such as from about 55 to 165%, from about 65 to 160%, from about 85 to 150%, or from about 90 to 125%, in comparison to a similarly prepared nonwoven fabric that does not include the secondary alkane sulfonate.

Nonwoven fabrics in accordance with embodiments of the present invention also exhibit increased toughness in comparison to a similarly prepared nonwoven fabric that does not include the secondary alkane sulfonate. The toughness of nonwoven fabrics may be compared by examining the product resulting from the multiplication of the observed percent elongation and the observed tensile strength of the fabric. The product of this multiplication is referred to as the Index of Toughness, which is approximately proportional to the area under the stress strain curve. As discussed below in the Test Methods section, all tensile and elongation values are obtained according to German Method 10 DIN 53857 in which a sample having a width of 5 cm and a 100 mm gauge length at a cross-head speed of 200 mm/min were recorded at peak. Since Index of Toughness results from the product of multiplying Tensile X % Elongation, the Index of Toughness has units of (N/5 cm)-%. Since all mechanical properties result from testing a 5 cm wide sample, the units for Index of Toughness in this document will be simplified to N-%.

Nonwoven fabrics in accordance with the present invention may exhibit an MD Index of Toughness that is from about 2,000 to 7,500 N-%, and in particular, from about 2,300 to 6,500, and more particularly, from about 2,300 to 6,000 N-%, and a CD Index of Toughness that is from about 1,000 to 5,000 N-%, and in particular, from about 1,250 to 5,000, and more particularly, from about 1,250 to 3,500 N-%.

In one embodiment, the inventive nonwoven fabric may exhibit an increase in MD Index of Toughness that is from 20 to 1,250% in comparison to a similarly prepared nonwoven fabric that does not include the secondary alkane sulfonate. For example, the inventive nonwoven fabric may exhibit an increase in MD Index of Toughness of any one or more of at least 25%, at least 100%, at least 200%, at least 300%, at least 400%, at least 500%, at least 600%, at least 700%, at least 800%, at least 900%, at least 1,000%, at least 1,050%, at least 1,100%, at least 1,150%, at least 1,200%, at least 1,250%, at least 1,300%, or at least 1,500%, in comparison to a similarly prepared nonwoven fabric that does not include the secondary alkane sulfonate.

In some embodiments, the inventive nonwoven fabric may exhibit an increase in CD Index of Toughness that is from about 50 to 1,000% in comparison to a similarly prepared nonwoven fabric that does not include the secondary alkane sulfonate. For example, the inventive nonwoven fabric may exhibit an increase in CD Index of Toughness of any one or more of at least 60%, at least 75%, at least 80%, at least 85%, at least 90%, at least 100%, at least 150%, at least 200%, at least 250%, at least 300%, at least 350%, at least 400%, at least 500%, at least 550%, at least 600%, at least 700%, at least 800%, at least 900%, at least 1,000%, or at least 1,025%, in comparison to a similarly prepared nonwoven fabric that does not include the secondary alkane sulfonate.

To account for variations in basis weights, it may also be useful to consider Relative Index of Toughness for the inventive nonwoven fabrics in comparison to similarly prepared nonwoven fabrics that do not include the secondary alkane sulfonate. The inventive nonwoven fabrics also exhibited significant increases in toughness in comparison to the nonwoven fabrics of the comparative examples. The Relative Index of Toughness is calculated from the Index of Toughness, which is then normalized for basis weight. The Toughness Index can be divided by basis weight to provide a normalized Index of Toughness with units of N-%/g/m2.

Nonwoven fabrics in accordance with the present invention may exhibit an MD Relative Index of Toughness that is from about 50 to 150 N-%/g/m2, and in particular, from about 75 to 125, and more particularly, from about 85 to 115 N-%/g/m2, and a CD Relative Index of Toughness that is from about 40 to 100 N-%/g/m2, and in particular, from about 45 to 85, and more particularly, from about 45 to 75 N-%/g/m2.

In one embodiment, the inventive nonwoven fabric may exhibit an increase in MD Relative Index of Toughness that is from 100 to 1000% in comparison to a similarly prepared nonwoven fabric that does not include the secondary alkane sulfonate. In a preferred embodiment, the inventive nonwoven fabric may exhibit an increase in MD Relative Index of Toughness that is from about 80 to 500%, and more preferably, from about 140 to 480% in comparison to a similarly prepared nonwoven fabric that does not include the secondary alkane sulfonate. For example, the inventive nonwoven fabric may exhibit an increase in MD Relative Index of Toughness of any one or more of at least 100%, at least 125%, at least 150%, at least 175%, at least 200%, at least 225%, at least 250%, at least 275%, at least 300%, at least 325%, at least 350%, at least 375%, at least 400%, at least 425%, at least 450%, at least 475%, at least 500%, at least 525%, at least 550%, at least 575%, at least 600%, at least 625%, at least 650%, at 675%, at least 700%, at least 725%, at least 750%, at least 775%, at least 800%, at least 825%, at least 850%, at least 875%, at least 900%, at least 925%, at least 950, at least 975%, or at least 1,000%, in comparison to a similarly prepared nonwoven fabric that does not include the secondary alkane sulfonate.

In one embodiment, the inventive nonwoven fabric may exhibit an increase in CD Relative Index of Toughness that is from 100 to 1000% in comparison to a similarly prepared nonwoven fabric that does not include the secondary alkane sulfonate. In a preferred embodiment, the inventive nonwoven fabric may exhibit an increase in CD Relative Index of Toughness that is from about 140 to 500%, and more preferably, from about 140 to 410% in comparison to a similarly prepared nonwoven fabric that does not include the secondary alkane sulfonate. For example, the inventive nonwoven fabric may exhibit an increase in MD Relative Index of Toughness of any one or more of at least 100%, at least 125%, at least 150%, at least 175%, at least 200%, at least 225%, at least 250%, at least 275%, at least 300%, at least 325%, at least 350%, at least 375%, at least 400%, at least 425%, at least 450%, at least 475%, at least 500%, at least 525%, at least 550%, at least 575%, at least 600%, at least 625%, at least 650%, at 675%, at least 700%, at least 725%, at least 750%, at least 775%, at least 800%, at least 825%, at least 850%, at least 875%, at least 900%, at least 925%, at least 950, at least 975%, or at least 1,000%, in comparison to a similarly prepared nonwoven fabric that does not include the secondary alkane sulfonate.

When comparing properties of different nonwovens it is often useful to compare the root mean square of the combined values of the MD and CD property of interest. This method allows comparison of single values. The root mean square provides a single number that combines input from both the MD and the CD values by taking the square root of the sum of the square of the MD value plus the square of the CD value. Use of the root mean square method to combine the MD and the CD results is particularly useful if samples to be compared were made on different machines or under some different condition that might influence the MD/CD ratio. The root mean square of the Toughness Index per basis weight is calculated with the following formula:

( ( MDTI ) 2 + ( CDTI ) 2 2 ) / Basis ⁢ weight

Where MDTI is the machine direction Toughness Index and CDTI is the cross direction Toughness Index.

Nonwoven fabrics in accordance with the invention may have a root mean square of the Toughness Index per basis weight that is at least 55 N-%/g/m2, and more preferably, at least 65 N-%/g/m2, and even more preferably at least 70 N-%/g/m2. In one embodiment, the fabric has a root mean square of the Toughness Index per basis weight has a value from about 55 to 250 N-%/g/m2, and in particular, from about 65 to 150 N-%/g/m2, and more particularly, from about 65 to 100 N-%/g/m2. In one embodiment, the fabric has a root mean square of the Toughness Index per basis weight of at least 75, at least 80, at least 85, at least 90, at least 95, at least 100, at least 105, at least 110, at least 115, at least, 120, at least 125, at least, 130, at least 135, at least 140, at least 145, at least 150, at least 155, at least 160, at least 165, at least 170, at least 175, at least 180, at least 185, at least 190, at least 195, and at least 200 N-%/g/m2.

By “similarly prepared nonwoven fabric” it should be understood the comparison nonwoven fabric has the identical polymer composition with the exception of the secondary alkane sulfonate, and that slight variations in processing conditions, such as temperature (e.g., extruder, calendaring, and die temperatures), draw speeds, and pressures may exist.

While not wishing to be bound by theory, it is believed that the presence of the secondary alkane sulfonate in the fibers may help improve bonding of fibers to each other, which results in improvements in the mechanical properties of the nonwoven fabric. In this regard, FIGS. 1A and 1B are SEM images of a nonwoven fabric taken at a magnification of 250× and 100×, respectively, and FIGS. 2A and 2B are SEM images of an nonwoven fabric in accordance with the present invention taken at a magnification of 250× and 100×, respectively. The fabric of FIGS. 1A and 1B are identical to the fabric of FIGS. 2A and 2B with the exception that the fabric of FIGS. 1A and 1B do not include a secondary alkane sulfonate. In both fabric, the fabric were point bonded with a calender roll.

The SEM images of the fabric of FIGS. 1A and 1B show that the individual fibers of the bond points were poorly bonded to each other. More specifically, it is observed that the fibers exhibited relatively poor melting and flowing of the polymer during bonding. In contrast, the SEM images of the fabric of FIGS. 2A and 2B exhibited good melting and flow of the polymer within each bond point. As can be seen in FIG. 2B, this resulted in each bond point exhibiting a film like appearance due to the melting and flowing of the polymer. The inventive fabric exhibited significant improvements in bonding in comparison to the fabric that did not include the secondary alkane sulfonate.

According to certain embodiments, for instance, the fabric may comprise a machine direction (MD) tensile strength at peak from about 25 N/5 cm to about 150 N/5 cm. In other embodiments, for example, the fabric may comprise a MD tensile strength at peak from about 50 N/5 cm to about 150 N/5 cm. In further embodiments, for instance, the fabric may comprise a MD tensile strength at peak from about 65 N/5 cm to about 90 N/5 cm. As such, in certain embodiments the fabric may comprise a MD tensile strength at peak from at least about any of the following: 25, 26, 27, 28, 29, 30, 50, 60, 70, 80, 100, 110, 120, 130 N/5 cm, and 140/5 cm, and/or at most about 175, 150, 145, 140, 130, 120 N/5 cm, and 110, 100, and 90 N/5 cm (e.g., about 25-175 N/5 cm, about 80-140 N/5 cm, etc.).

In certain embodiments, for example, the fabric may comprise a cross machine direction (CD) tensile strength at peak from about 20 N/5 cm to about 85 N/5 cm. In other embodiments, for instance, the fabric may comprise a CD tensile strength at peak from about 25 N/5 cm to about 75 N/5 cm. In some embodiments, for example, the fabric may comprise a CD tensile strength at peak from about 29 N/5 cm to about 74 N/5 cm. As such, in certain embodiments, the fabric may comprise a CD tensile strength at peak from at least about any of the following: 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, and 30 N/5 cm and/or at most about 85, 80, 75, 70, 65, 60, and 50 N/5 cm (e.g., about 20-85 N/5 cm, about 25-75 N/5 cm, etc.).

According to certain embodiments, for instance, the fabric may comprise an MD elongation percentage at peak from about 20% to about 50%. In other embodiments, for example, the fabric may comprise an MD elongation percentage at peak from about 25% to about 45%. In further embodiments, for instance, the fabric may comprise an MD elongation percentage at peak from about 28% to about 41%. As such, in certain embodiments, the fabric may comprise an MD elongation percentage at peak from at least about any of the following: 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40% and/or at most about 50, 45, 44, 43, 42, 41, 40, 39, 38, 37, 36, 35, 34, 33, 32, 31, and 30% (e.g., about 20-50%, about 21-45%, etc.).

In certain embodiments, for example, the fabric may comprise a CD elongation percentage at peak from about 30% to about 75%. In other embodiments, for instance, the fabric may comprise a CD elongation percentage at peak from about 35% to about 60%. In some embodiments, for example, the fabric may comprise a CD elongation percentage at peak from about 40% to about 50%. As such, in certain embodiments, the fabric may comprise an CD elongation percentage at peak from at least about any of the following: 10, 15, 20, 25, 30, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, and 49% and/or at most about 55, 50, 49, 48, and 47% (e.g., about 10-55%, about 15-50%, etc.).

In accordance with certain embodiments, particular processes may be used to prepare the PLA spunbond nonwoven fabrics. In such embodiments, the process may include providing a stream of molten or semi-molten PLA resin that includes at least one secondary alkane sulfonate, forming a plurality of drawn PLA continuous filaments, depositing the plurality of PLA continuous filaments onto a collection surface, exposing the plurality of PLA continuous filaments to ions, and bonding the plurality of PLA continuous filaments to form the PLA spunbond nonwoven fabric. According to certain embodiments, for example, forming the plurality of PLA continuous filaments may comprise spinning the plurality of PLA continuous filaments, drawing the plurality of PLA continuous filaments, and randomizing the plurality of PLA continuous filaments.

In this regard, the spunbond nonwoven web may be produced, for example, by the conventional spunbond process wherein molten polymer is extruded into continuous filaments which are subsequently quenched, attenuated or drawn mechanically by draw rolls or pneumatically by a high velocity fluid, and collected in random arrangement on a collecting surface. After filament collection, any thermal, chemical or mechanical bonding treatment may be used to form a bonded web such that a coherent web structure results.

In accordance with certain embodiments, for instance, the process may occur at a fiber draw speed greater than about 2500 m/min. In other embodiments, for example, the process may occur at a fiber draw speed from about 3000 m/min to about 4000 m/min. In further embodiments, for instance, the process may occur at a fiber draw speed from about 3000 m/min to about 5500 m/min. As such, in certain embodiments, the process may occur at a fiber draw speed from at least about any of the following: 2501, 2550, 2600, 2650, 2700, 2750, 2800, 2850, 2900, 2950, and 3000 m/min and/or at most about 5500, 4000, 3950, 3900, 3850, 3800, 3750, 3700, 3650, 3600, 3550, and 3500 m/min (e.g., about 2700-3800 m/min, about 3000-3700 m/min, etc.).

In accordance with certain embodiments, for instance, bonding the web to form the PLA spunbond nonwoven fabric may comprise thermal point bonding the web with heat and pressure via a calender having a pair of cooperating rolls including a patterned roll. In such embodiments, for example, thermal point bonding the web may comprise imparting a three-dimensional geometric bonding pattern onto the PLA spunbond nonwoven fabric. The patterned roll may comprise a three-dimensional geometric bonding pattern. In some embodiments, for example, the bonding pattern at least one of a diamond pattern, a hexagonal dot pattern, an oval-elliptic pattern, a rod-shaped pattern, or any combination thereof. In some embodiments, the calender may include a release coating to minimize deposit of molten or semi molten polymer on the surface of one or more of the rolls. As an example, such release coating is described in European Patent Application No. 1,432,860, which is incorporated herein in its entirety by reference.

In accordance with certain embodiments, for instance, the process may further comprise dissipating static charge from the PLA spunbond nonwoven fabric proximate to the calender via the static control unit. In some embodiments, for example, the static control unit may comprise an ionization source. In further embodiments, for instance, the ionization source may comprise an ionization bar. However, in other embodiments, for example, dissipating static charge from the PLA spunbond nonwoven fabric may comprise contacting the PLA spunbond nonwoven fabric with a static bar.

In accordance with certain embodiments, for instance, the process may further comprise cutting the PLA spunbond nonwoven fabric to form cut PLA spunbond nonwoven fabric, exposing the cut PLA spunbond nonwoven fabric to ions via a third ionization source, and winding the cut PLA spunbond nonwoven fabric into rolls. In such embodiments, for example, the third ionization source may comprise an ionization bar.

In accordance with certain embodiments, for instance, the process may further comprise increasing humidity while forming the plurality of PLA continuous filaments. In such embodiments, for example, increasing humidity may comprise applying at least one of steam, fog, mist, or any combination thereof to the plurality of PLA continuous filaments.

Certain embodiments according to the invention provide systems for preparing a PLA spunbond nonwoven fabric. In accordance with certain embodiments, the system includes a first PLA source configured to provide a stream of molten or semi-molten PLA resin, a source of at least one secondary alkane sulfonate that is configured to introduce the at least one secondary alkane sulfonate into the PLA source, a spin beam in fluid communication with the first PLA source, a collection surface disposed below an outlet of the spin beam onto which the PLA continuous filaments are deposited to form the PLA spunbond nonwoven fabric, a first ionization source positioned and arranged to expose the PLA continuous filaments to ions, and a calender positioned downstream of the first ionization source. The spin beam, according to certain embodiments, is configured to extrude and draw a plurality of PLA continuous filaments.

In this regard, the spunbond nonwoven web may be produced, for example, by the conventional spunbond process on spunbond machinery such as, for example, the Reicofil-3 line or Reicofil-4 line from Reifenhauser, as described in U.S. Pat. No. 5,814,349 to Geus et al, the entire contents of which are incorporated herein by reference, wherein molten polymer is extruded into continuous filaments which are subsequently quenched, attenuated pneumatically by a high velocity fluid, and collected in random arrangement on a collecting surface. In some embodiments, the continuous filaments are collected with the aid of a vacuum source positioned below the collection surface. After filament collection, any thermal, chemical or mechanical bonding treatment may be used to form a bonded web such that a coherent web structure results. As one skilled in the art will understand, examples of thermal bonding may include thru-air bonding where hot air is forced through the web to soften the polymer on the outside of certain fibers in the web followed by at least limited compression of the web or calender bonding where the web is compressed between two rolls, at least one of which is heated, and typically one is an embossed roll.

In some embodiments, for instance, the collection surface may comprise conductive fibers. The conductive fibers may comprise monofilament wires made from polyethersulfone conditioned with polyamide (e.g., Huycon—LX 135). In the machine direction, the fibers comprise polyamide conditioned polyethersulfone. In the cross-machine direction, the fibers comprise polyamide conditioned polyethersulfone in combination with additional polyethersulfone.

With reference to FIG. 3, for example, a schematic diagram of the PLA spunbond nonwoven fabric preparation system in accordance with certain embodiments of the invention is illustrated.

As shown in FIG. 3, a PLA source (i.e. hopper) 2 is in fluid communication with the spin beam 4 via the extruder 6. At least one secondary alkane sulfonate is then blended with PLA resin in the extruder 6 to provide a molten or semi-molten PLA stream that is introduced into the spin beam 4. It should be noted that the secondary alkane sulfonate may be introduced directly into the extruder or may be introduced into the PLA source (e.g., the hopper) prior to the PLA resin being introduced into the extruder.

Although FIG. 3 illustrates an embodiment having two PLA sources 2 and two extruders 6, the system may include any number of polymer sources (e.g., PLA, synthetic polymer, such as polypropylene, polyethylene, etc.) and extruders as dictated by a particular application as understood by one of ordinary skill in the art. Following extrusion, the extruded polymer may then enter a plurality of spinnerets (not shown) for spinning into filaments. Following spinning, the spun filaments may then be drawn (i.e. attenuated) via a drawing unit (not shown) and randomized in a diffuser (28 in FIGS. 4A-4C). The spin beam 4 produces a curtain of filaments (30 in FIGS. 4A-4C) that is deposited on the collection surface 10 at point 8.

In one embodiment, the thus deposited filaments may then be bonded to form a coherent web. In some embodiments, a pair of cooperating rolls 12 (also referred to herein as a “press roll”) stabilize the web of the PLA continuous filaments by compressing the web before delivery to the calender 14 for bonding. In some embodiments, for example, the press roll may include a ceramic coating deposited on a surface thereof. In certain embodiments, for instance, one roll of the pair of cooperating rolls 12 may be positioned above the collection surface 10, and a second roll of the pair of cooperating rolls 12 may be positioned below the collection surface 10. Finally, the bonded PLA spunbond nonwoven fabric moves to a winder 16, where the fabric is wound onto rolls.

During the course of their investigation, the inventors have discovered that static generation during fiber spinning and web processing when PLA is exposed on the fiber surface promotes web wraps at the press rolls and calender of the spunbond machine. This web wrap is undesirable and generally has prevented the high speed production of fabrics comprising 100% PLA, or fabrics in which PLA is exposed at the surface of the fibers. One method of addressing web wrap is by increasing the humidity of the spunbond process by, for example, injecting steam into the air stream used to quench the just-spun fibers or providing a fine mist or fog of moisture around the press rolls where the spun fibers are first formed into an unbonded web. Although the extra humidity provides some protection from web wraps, the addition of high moisture over a period of time may promote corrosion of the spunbond machine and growth of mold or microorganisms detrimental to nonwoven use in hygiene and medical operations.

Another method of reducing static charge build up in the nonwoven fabric is to contact the web where the PLA is exposed on the surface of the fiber with a conductive static bar, which helps to ground the web, thereby dissipating charge build-up. However, this approach requires direct contact between the nonwoven web and the conductive substrate, and at such contact points there remains the possibility of direct discharge of static electricity through space with resulting possible harm to the operator, damage to equipment and risk of fire.

Advantageously, the inventors have discovered that fabrics comprising 100% PLA may be prepared at commercially viable processing speeds by positioning one or more ionization sources in close proximity to the nonwoven fabric. For example, in one embodiment, an ionization source 18 may be positioned near the spin beam 4 and the winder 16 to actively dissipate/neutralize static charge without contacting the fabric. As explained below, the ionization source exposes the nonwoven fabric to a stream of ions, which act to neutralize static charges in the nonwoven fabric. The stream of ions may include positive ions, negative ions, and combinations thereof.

In some embodiments, it may also be desirable to position a static control unit 20 near the calender 14. The static control unit 20 may be a passive static bar requiring contact with the fabric or an active ionization bar, which does not require contact with the fabric. Finally, an optional humidity unit 26 may be used in conjunction with the spin beam 4 and/or the press roll 12 to reduce static via added moisture.

In accordance with certain embodiments, for example, the first ionization source may be positioned above the collection surface and downstream of a point at where the PLA continuous filaments are deposited on the collection surface. However, in other embodiments, for instance, the first ionization source may be positioned between the outlet of the spin beam and the collection surface.

As discussed previously, the system may further comprise a press roll positioned downstream from the outlet of the spin beam. In this regard, the press roll may be configured to stabilize the web of the PLA continuous filaments by compressing said web before delivery of the PLA continuous fibers from the outlet of the spin beam towards the calender. In those embodiments including the press roll, for example, the first ionization source may be positioned downstream from the press roll. In other embodiments, for instance, the first ionization source may be positioned between the spin beam and the press roll.

In some embodiments and as shown in FIG. 3, the system may comprise a vacuum source 24 disposed below the collection surface for pulling the plurality of PLA continuous filaments from the outlet of the spin beam onto the collection surface before delivery to the calender.

FIGS. 4A-4C, for example, are schematic diagrams illustrating positioning of the first ionization source in accordance with certain embodiments of the invention. As shown in FIG. 4A, the first ionization source 18 is positioned downstream of the outlet (i.e. diffuser) 28 of the spin beam 4 but upstream of the press roll 12. In FIG. 4B, however, the first ionization source 26 is positioned downstream of the press roll 12. In FIG. 2C, the first ionization source is positioned downstream of the point 8 at which the curtain of filaments 30 are deposited on the collection surface but also within the outlet 46.

Preferably, the ionization source comprises a device that is capable of actively discharging ions with the use of electrodes, ionizing air nozzles, ionizing air blowers, and the like. In one embodiment, the ionization source comprises an active discharge ionization bar that actively discharges ions in the direction of the nonwoven fabric. Examples of suitable ionization bars may include Elektrostatik Discharging Electrode E3412, which is available from Iontis.

In one embodiment, the ionization bar may extend over the web in the cross direction. Preferably, the ionization bar extends in the cross direction across the total width of the nonwoven fabric. In further embodiments, the ionization bar may extend under the web and the collection surface in the cross direction. However, positioning the ionization bar under the collection surface may be less effective than positioning the ionization bar over the web in the cross direction.

According to certain embodiments, for example, the first ionization source and the collection surface may be separated by a distance from about 1 inch to about 24 inches. In other embodiments, for instance, the first ionization source and the collection surface may be separated by a distance from about 1 inch to about 12 inches. In further embodiments, for example, the first ionization source and the collection surface may be separated by a distance from about 1 inch to about 5 inches. As such, in certain embodiments, the first ionization source and the collection surface may be separated by a distance from at least about any of the following: 1, 1.25, 1.5, 1.75, and 2 inches and/or at most about 24, 20, 16, 12, 10, 9, 8, 7, 6, and 5 inches (e.g., about 1.5-10 inches, about 2-8 inches, etc.).

In accordance with certain embodiments, for instance, the system may further comprise a static control unit positioned and arranged to dissipate static from the PLA spunbond nonwoven fabric proximate to the calender. In some embodiments, for example, the static control unit may be positioned upstream from, and adjacent to, the calender. In other embodiments, however, the static control unit may be positioned downstream from, and adjacent to, the calender.

In some embodiments, for instance, the static control unit may comprise a passive static bar. In such embodiments, the static control unit may contact the PLA spunbond nonwoven fabric in order to dissipate static charge. In other embodiments, however, the static control unit may comprise a second ionization source. As such, the second ionization source may actively dissipate static charge from the PLA spunbond nonwoven fabric such that contact by the second ionization source with the PLA spunbond nonwoven fabric is not required in order to dissipate the static charge.

According to certain embodiments, for example, the system may further comprise a winder positioned downstream from the calender. In such embodiments, for instance, the system may also include a third ionization source positioned and arranged to expose the PLA spunbond nonwoven fabric to ions proximate to the winder. In some embodiments, for example, at least one of the first ionization source, the static control source (e.g., the second ionization source), and the third ionization source may comprise an ionization bar. In this regard, for instance, the first ionization source, the static control source, and the third ionization source may be configured to actively dissipate static charge created during preparation of the PLA spunbond nonwoven fabric.

In accordance with certain embodiments, for example, the system may further comprise a humidity unit positioned within or downstream from the spin beam. In such embodiments, for instance, the humidity unit may comprise at least one of a steam unit, a fogging unit, a misting unit, or any combination thereof. In this regard, for example, humidity may be added in the spin beam during the formation of the plurality of PLA continuous filaments and/or near the press roll(s) (in those embodiments utilizing at least one press roll) in order to provide additional management of static charge that develops during the production of the PLA spunbond nonwoven fabric.

Nonwoven fabrics in accordance with embodiments of the invention may be used to prepare a variety of different structures. For example, in some embodiments, the inventive nonwoven fabric may be combined with one or more additional layers to prepare a composite or laminate material. Examples of such composites/laminates may include a spunbond composite, a spunbond-meltblown (SM) composite, a spunbond-meltblown-spunbond (SMS) composite, or a spunbond-meltblown-meltblown-spunbond (SMMS) composite. In some embodiments, composites may be prepared comprising a layer of the inventive nonwoven fabric and one or more film layers.

For example, FIGS. 5A-5D are cross-sectional views of composites in accordance with certain embodiments of the invention. For example, FIG. 5A illustrates a spunbond-meltblown (SM) composite 50 having a PLA spunbond nonwoven fabric layer 52 in accordance with embodiments of the present invention, and a meltblown layer 54. FIG. 5B illustrates a spunbond-meltblown-spunbond (SMS) composite 56 having two PLA spunbond nonwoven fabric layers 52 and a meltblown layer 54 sandwiched between the PLA spunbond nonwoven fabric layers 52. FIG. 5C illustrates an SMS composite 58 having a PLA spunbond nonwoven fabric layer 52, a different spunbond layer 60, and a meltblown layer 54 sandwiched between the two spunbond layers 52, 6. Finally, FIG. 4D illustrates a spunbond-meltblown-meltblown-spunbond (SMMS) composite 62 having a PLA spunbond nonwoven fabric layer 52, a different spunbond layer 60, and two meltblown layers 54 sandwiched between the two spunbond layers 52, 60. Although the SMMS composite 62 is shown as having two different spunbond layers 52 and 60, both spunbond layers may be the PLA spunbond nonwoven fabric layer 52.

In these multilayer structures, the basis weight of the PLA spunbond nonwoven fabric layer may range from as low as 7 g/m2 and up to 150 g/m2. In such multilayered laminates, both the meltblown and spunbond fibers could have PLA on the surface to insure optimum bonding. In some embodiments in which the spunbond layer is a part of a multilayer structure (e.g., SM, SMS, and SMMS), the amount of the meltblown in the structure may range from about 5 to 30%, and in particular, from about 5 to 15% of the structure as a percentage of the structure as a whole.

Multilayer structures in accordance with embodiments can be prepared in a variety of manners including continuous in-line processes where each layer is prepared in successive order on the same line, or depositing a meltblown layer on a previously formed spunbond layer. The layers of the multilayer structure can be bonded together to form a multilayer composite sheet material using thermal bonding, mechanical bonding, adhesive bonding, hydroentangling, or combinations of these. In certain embodiments, the layers are thermally point bonded to each other by passing the multilayer structure through a pair of calender rolls.

In yet another aspect, certain embodiments of the invention provide absorbent articles. In accordance with certain embodiments, the absorbent article may include a nonwoven fabric in accordance with the present invention. In one embodiment, a sustainable composite may be provided that includes at least two nonwoven fabric layers such that at least one nonwoven fabric layer may comprise a PLA spunbond nonwoven fabric layer in which a secondary alkane sulfonate is incorporated. The PLA spunbond nonwoven fabric layer may comprise a plurality of fibers such that PLA may be present at a surface of the plurality of fibers. In some embodiments, the absorbent article may be sustainable, but the sustainability of the absorbent article depends upon the other materials incorporated into the absorbent article other than the sustainable composite.

In this regard, fabrics prepared in accordance with embodiments of the invention may be used in wide variety of articles and applications. For instance, embodiments of the invention may be used for personal care applications, for example products for babycare (diapers, wipes), for femcare (pads, sanitary towels, tampons), for adult care (incontinence products), or for cosmetic applications (pads), agricultural applications, for example root wraps, seed bags, crop covers, industrial applications, for example work wear coveralls, airline pillows, automobile trunk liners, sound proofing, and household products, for example mattress coil covers and furniture scratch pads.

FIG. 6A, for example, is an illustration of an absorbent article (shown here as a diaper) in accordance with at least one embodiment of the invention and broadly designated by reference numeral 70. The diaper 70 may include an absorbent core 74. FIG. 6B is a cross-sectional view of the diaper 70 of FIG. 5A taken along line 72-72 of FIG. 5A. As shown in FIG. 6B, the absorbent core 74 may be sandwiched between a topsheet 80 and a backsheet 82. As further discussed herein, one or both of the topsheet 80 and the backsheet 82 may comprise a PLA spunbond nonwoven fabric and/or a sustainable composite including a PLA spunbond nonwoven fabric layer as previously discussed in more detail herein.

The topsheet 30 is positioned adjacent an outer surface of the absorbent core 74 and is preferably joined thereto and to the backsheet 82 by attachment means (not shown) such as those well known in the art. For example, the topsheet 80 may be secured to the absorbent core 74 by a uniform continuous layer of adhesive, a patterned layer of adhesive, or an array of separate lines, spirals, or spots of adhesive.

As used herein, the term “joined” encompasses configurations whereby an element is directly secured to the other element by affixing the element directly to the other element, and configurations whereby the element is indirectly secured to the other element by affixing the element to intermediate member(s) which in turn are affixed to the other element. In a preferred embodiment of the present invention, the topsheet 80 and the backsheet 82 are joined directly to each other in the diaper periphery 86 and are indirectly joined together by directly joining them to the absorbent core 74 by the attachment means (not shown).

Preferably, the topsheet 80 is compliant, soft feeling, and non-irritating to the wearer's skin. Further, the topsheet 80 is liquid pervious permitting liquids (e.g., urine) to readily penetrate through its thickness. A suitable topsheet may be manufactured from a wide range of materials, such as porous foams; reticulated foams; apertured plastic films; or woven or nonwoven webs of natural fibers (e.g., wood or cotton fibers), or a combination of natural and synthetic fibers.

In some embodiments, the topsheet may be treated with a surfactant to help ensure proper liquid transport through the topsheet and into the absorbent core. An example of a suitable surfactant is available from Momentive Performance Materials under the tradename NUWET™ 237.

In one embodiment, at least one of the topsheet and backsheet comprises a nonwoven fabric comprising PLA continuous filaments that includes a secondary alkaline sulfonate as discussed previously.

In a preferred embodiment, the topsheet comprises at least 75 weight percent of bio-based materials, such as at least 75 weight percent of the inventive PLA spunbond nonwoven fabric. Additional examples of bio-based polymers that may be used in embodiments of the invention include polymers directly produced from organisms, such as polyhydroxyalkanoates (e.g., poly(beta-hydroxyalkanoate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate, NODAX™), and bacterial cellulose; polymers extracted from plants and biomass, such as polysaccharides and derivatives thereof (e.g., gums, cellulose, cellulose esters, chitin, chitosan, starch, chemically modified starch), proteins (e.g., zein, whey, gluten, collagen), lipids, lignins, and natural rubber; and current polymers derived from naturally sourced monomers and derivatives, such as bio-polyethylene, bio-polypropylene, polytrimethylene terephthalate, polylactic acid, NYLON 11, alkyd resins, succinic acid-based polyesters, and bio-polyethylene terephthalate.

There are a number of manufacturing techniques which may be used to manufacture the topsheet 80. For example, the topsheet 80 may be a nonwoven web of fibers. When the topsheet comprises a nonwoven web, the web may be spunbonded, carded, wet-laid, meltblown, hydroentangled, combinations of the above, or the like. A preferred topsheet comprises a spunbond nonwoven fabric in which the fibers are thermally bonded to each other to form a coherent web.

The backsheet 82 is positioned adjacent to an opposite surface of the absorbent core 74 and is preferably joined thereto by attachment mechanisms (not shown) such as those well known in the art. Suitable attachment mechanisms are described with respect to joining the topsheet 80 to the absorbent core 74. Alternatively, the attachment means may comprise heat bonds, pressure bonds, ultrasonic bonds, dynamic mechanical bonds, or any other suitable attachment means or combinations of these attachment mechanisms as are known in the art.

The backsheet 82 is impervious to liquids (e.g., urine) and is preferably manufactured from a thin plastic film, although other flexible liquid impervious materials may also be used. As used herein, the term “flexible” refers to materials which are compliant and will readily conform to the general shape and contours of the human body. The backsheet 82 prevents the exudates absorbed and contained in the absorbent core 74 from wetting articles which contact the diaper 70 such as bedsheets and undergarments. The backsheet 82 may thus comprise a woven or nonwoven material, polymeric films such as thermoplastic films, or composite materials such as a film-coated nonwoven material.

In some embodiments, material for the backsheet may include the bio-based polymers discussed previously, and in particular, the inventive PLA spunbond fabric described herein. In some embodiments, the backsheet may include additional bio-based polymers. For example, bio-based polymers for use in the backsheet may include polymers directly produced from organisms, such as polyhydroxyalkanoates (e.g., poly(beta-hydroxyalkanoate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate, NODAX™), and bacterial cellulose; polymers extracted from plants and biomass, such as polysaccharides and derivatives thereof (e.g., gums, cellulose, cellulose esters, chitin, chitosan, starch, chemically modified starch), proteins (e.g., zein, whey, gluten, collagen), lipids, lignins, and natural rubber; and current polymers derived from naturally sourced monomers and derivatives, such as bio-polyethylene, bio-polypropylene, polytrimethylene terephthalate, polylactic acid, NYLON 11, alkyd resins, succinic acid-based polyesters, and bio-polyethylene terephthalate.

In one embodiment, the backsheet may comprise a laminate structure having a liquid impervious film layer that is joined to a nonwoven web. Suitable films may be prepared from the bio-based polymers as previously discussed. In one example, the film may comprise a sugar cane derived polyethylene polymer, such as a film grade LDPE polyethylene grade SEB853/72 or SPB681/59 recommended by Braskem S. A. for lamination. Suitable films may also include additives such as CaCO3 to improve film breathability while still maintaining fluid barrier properties. In some embodiments, the backsheet layer may comprise a laminate structure having a bio-based film layer, such as those discussed previously, that is laminated to a fabric layer having a spunbond-meltblown-spunbond (SMS) structure.

The absorbent core 74 may comprise any material that is capable of absorbing fluids and exudates. Preferably, the absorbent core comprises at least 75% by weight of bio-based materials. In one embodiment, materials for the core wrap may comprise a fabric layer comprising a spunbond fabric, spunbond-meltblown fabric (SM), or an SMS fabric. An example of a core wrap comprising an SMS fabric comprises a spunbond nonwoven layer comprising bicomponent fibers having a PLA sheath (e.g., Nature Works PLA Grade PLA 6752 with 4% D Isomer), and a PLA core (e.g. NatureWorks Grade 6202 with 2% D Isomer). In one embodiment, the meltblown layer of the SMS fabric may be comprised of a PLA meltblown fibers (e.g., NatureWorks PLA grade 6252).

FIG. 7 is an illustration of an absorbent article in accordance with at least one embodiment of the invention in which the absorbent article is in the form of a feminine sanitary pad broad designated by reference numeral 100. Pad 100 may include a topsheet 102, backsheet 104, and an absorbent core 106 disposed there between. Preferably, topsheet 102 and backsheet 104 are joined to each other about along opposing outer edges to define a continuous seam 108 that extends about the periphery 110 of the pad 100. Continuous seam 108 may comprise a heat seal that is formed from thermally bonding the topsheet and backsheet to each other. In other embodiments, continuous seam 108 is formed by adhesively bonding the topsheet and backsheet to each other.

As in the embodiments discussed above, pad 100 preferably comprises a nonwoven fabric in accordance with the present invention. That is a spunbond nonwoven fabric comprising fibers that are a blend of a PLA resin and a secondary alkaline sulfonate.

In some embodiments, the pad 100 may comprise a sustainable articles comprising a bio-based material content of at least 75 weight percent, based on the total weight of the pad, such as comprising a bio-based material content that is at least 80%, 85%, 90%, or 95% by weight of the pad. Suitable materials for the topsheet, backsheet, and absorbent core are discussed previously.

In some embodiments, pad 100 may also include a fluid acquisition layer 112 that is disposed between the absorbent core 106 and the topsheet 102. In one embodiment a fluid acquisition layer could be made by carding a web comprised of a blend of 7 denier hollow PLA-Type 820 2 inch cut length staple fibers plus 3 denier Solid PLA-Type 821 2 inch cut length staple fibers, (both available from Fiber Innovations Technology—Johnson City, Tenn.); treating the resulting carded web via kiss roll with a suspension of cooked starch (for example type STABITEX 65401 from Cargill); exposing the resulting web of fiber and starch to elevated temperature via a combination of hot air and contact to heated dryer cans to cure and dry the web, and winding and slitting the resulting roll in to child rolls for use in the absorbent article.

Various components of the absorbent article are typically joined via thermal or adhesive bonding. When an adhesive is employed, the adhesive preferably comprises a bio-based adhesive. An example of a bio-based adhesive is a pressure sensitive adhesive available from Danimer Scientific under the product code 92721.

In accordance with certain embodiments, for example, at least the PLA spunbond nonwoven fabric layer may comprise bicomponent fibers. In some embodiments, for instance, the bicomponent fibers may comprise a side-by-side arrangement. However, in other embodiments, for example, the bicomponent fibers may comprise a sheath and a core. In further embodiments, for instance, the bicomponent fibers may comprise reverse bicomponent fibers. In certain embodiments, for example, the sheath may comprise PLA. In further embodiments, for instance, the core may comprise at least one of a polyolefin, a polyester, or any combination thereof. In some embodiments, for example, the core may comprise at least one of a polypropylene, a polyethylene, a polyethylene terephthalate, PLA, or any combination thereof. In certain embodiments, for instance, each of the sheath and the core may comprise PLA.

According to certain embodiments, for example, the sheath may comprise a first PLA grade, the core may comprise a second PLA grade, and the first PLA grade and the second PLA grade may be different. In some embodiments, for instance, the first PLA grade may comprise up to about 5% crystallinity, and the second PLA grade may comprise from about 40% to about 50% crystallinity. In other embodiments, for example, the first PLA grade may comprise a melting point from about 125° C. to about 135° C., and the second PLA grade may comprise a melting point from about 155° C. to about 170° C. In further embodiments, for instance, the first PLA grade may comprise a weight percent of D isomer from about 4 wt. % to about 10 wt. %, and the second PLA grade may comprise a weight percent of D isomer of about 2 wt. %. In some embodiments, for example, the bicomponent fibers may comprise about 70 wt. % core and about 30 wt. % sheath.

However, in other embodiments, for instance, at least the PLA spunbond nonwoven fabric layer may comprise a plurality of monocomponent PLA fibers comprising a blend of a PLA resin and a secondary alkane sulfone.

In a preferred embodiment, the PLA nonwoven fabric in accordance with the present invention may be used to manufacture sustainable absorbent articles. Examples of sustainable absorbent articles may be found in U.S. patent application Ser. No. 14/839,026 to Chester et al., incorporated fully by referenced herein.

As described in Chester et al., embodiments of absorbent articles have a high bio-based material content Preferably, absorbent articles in accordance with the embodiments of the present invention have a bio-based material content of at least 75 weight % of the absorbent article, such as comprising a bio-based material content that is at least 80%, 85%, 90%, or 95% by weight of the absorbent article. Chester et al. also describes that the absorbent articles may include a topsheet and a backsheet. In some embodiments, the absorbent articles may also include an absorbent core.

In one aspect, embodiments of the invention are directed to absorbent articles comprising a topsheet, a backsheet, and an absorbent core sandwiched therebetween. Preferably, the topsheet and backsheet are attached to each other along opposing surfaces to define a cavity in which the absorbent core is enclosed. As noted above, the components of absorbent article are selected so that at least 75% of the material comprising the absorbent article comprises a bio-based material, and preferably at least 80%, 85%, 90%, and 95% of the material comprising the absorbent article comprises a bio-based material.

Preferably, the absorbent article is substantially free of synthetic materials, such as petroleum-based materials and polymers. For example, absorbent articles in accordance with the present invention have less than 25 weight percent of materials that are non-bio-based, and more preferably, less than 20 weight percent, less than 15 weight percent, less than 10 weight percent, and even more preferably, less than 5 weight percent of non-bio-based materials, based on the total weight of the absorbent article.

Examples of absorbent articles in accordance with embodiments of the present invention include pant type absorbent articles, such as diapers, pull-ups, sanitary pants, and incontinence pants, and feminine absorbent articles, such as sanitary napkins. In one embodiment, the present invention is directed to disposable absorbent articles, such as disposable diapers.

Preferably, the topsheet is compliant, soft feeling, and non-irritating to the wearer's skin. Further, the topsheet is liquid pervious permitting liquids (e.g., urine) to readily penetrate through its thickness. A suitable topsheet may be manufactured from a wide range of materials, such as porous foams; reticulated foams; apertured plastic films; or woven or nonwoven webs of natural fibers (e.g., wood or cotton fibers), or a combination of natural and synthetic fibers.

In one embodiment, the topsheet is made of a hydrophobic material to help isolate the wearer's skin from liquids contained in the absorbent core.

In some embodiments, the topsheet may be treated with a surfactant to help ensure proper liquid transport through the topsheet and into the absorbent core. An example of a suitable surfactant is available from Momentive Performance Materials under the tradename NUWET™ 237.

Preferably, the topsheet comprises at least 75 weight percent of bio-based materials. Nonlimiting examples of bio-based polymers include polymers directly produced from organisms, such as polyhydroxyalkanoates (e.g., poly(beta-hydroxyalkanoate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate. NODAX™), and bacterial cellulose; polymers extracted from plants and biomass, such as polysaccharides and derivatives thereof (e.g., gums, cellulose, cellulose esters, chitin, chitosan, starch, chemically modified starch), proteins (e.g., zein, whey, gluten, collagen), lipids, lignins, and natural rubber; and current polymers derived from naturally sourced monomers and derivatives, such as bio-polyethylene, bio-polypropylene, polytrimethylene terephthalate, polylactic acid, NYLON 11, alkyd resins, succinic acid-based polyesters, and bio-polyethylene terephthalate.

In a preferred embodiment, the bio-based polymers include polylactic acid and bio-based derived polyethylene. Generally, polylactic acid based polymers are prepared from dextrose, a source of sugar, derived from field corn. In North America corn is used since it is the most economical source of plant starch for ultimate conversion to sugar. However, it should be recognized that dextrose can be derived from sources other than corn. Sugar is converted to lactic acid or a lactic acid derivative via fermentation through the use of microorganisms. Thus besides corn other agricultural based sugar source could be used including sugar beets, sugar cane, wheat, cellulosic materials, such as xylose recovered from wood pulping, and the like. Similarly, bio-based polyethylene can be prepared from sugars that are fermented to produce ethanol, which in turn is dehydrated to provide ethylene.

In one embodiment, the topsheet may comprise a nonwoven web comprising spunbond bicomponent fibers in which the fibers have a sheath-core configuration. In a preferred embodiment, the topsheet comprises spunbond bicomponent fibers having a core comprised of corn based polylactic acid (PLA), and a sheath comprising a sugar cane derived polyethylene polymer thus providing a topsheet of nearly 100% bio-based content. For use as a topsheet, such fabrics may desirably be treated with a surfactant such as suggested above to provide a hydrophilic surface Nonwoven fabrics comprising PLA and bio-based polyethylene with basis weights of 13.5 GSM and 17 GSM, respectively, Grades 040RXEO09P and 050RXE009P, surfactant treated to achieve a hydrophilic surface, are available from Fitesa Nonwovens of Simpsonville, S.C., 29681 USA.

An example of a suitable PLA polymer for the fiber core in such spunbond bicomponent fabrics is available from NatureWorks under the product name PLA Grade 6202. An example of a suitable sugar cane derived polyethylene is available from Braskem S. A. under the product name PE SHA7260. Advantageously, a topsheet comprising spunbond bicomponent fibers having a PLA core and a sheath comprising a sugar cane derived polyethylene polymer provides mechanical strength from the PLA core and improved softness from the polyethylene sheath.

In another embodiment, the polyethylene sheath of the bicomponent fiber may be replaced with a petroleum based polypropylene polymer to provide a topsheet with 50% bio-based content. Preferred polypropylenes for use in this embodiment will typically have a melt flow rate (MFR) between 20 to 40 g/10 min (measured in accordance with ASTM D1238 (190° C./2.16 kg)) such as for example provided by Total Petrochemicals and Refining USA, Inc. of La Port, Tex., 77571 USA as grades M 3766 (metallocene polypropylene) and 3764 or 3866 (Zeigler Natta polypropylene). Such Nonwovens, comprised of PP/PLA and showing 50% bio-based content, are available with basis weights of 13.5 GSM and 17 GSM as Grades 04PXBO09P and 050PXBG09P, respectively from Fitesa Nonwovens of Simpsonville, S.C., 29681 USA.

Further examples of nonwoven fabrics which after surfactant treatment can be used as topsheet in accordance with embodiments of the present invention include nonwoven webs, providing 50% bio-based content, comprising spunbond bicomponent fibers in which the core comprises a lignin based polymer and a sheath comprising a petroleum based polyethylene. Examples of such fabrics are disclosed as examples 4, 5, 6, 7, 8, and 9 in European Patent No. EP 2,630,285 BI and U.S. Patent Publication No. 2014/0087618. Substitution of the petroleum based polyethylene sheath in these examples with a sheath comprised of either the sugar cane derived polyethylene available from Braskem S. A. or the corn derived PLA available from NatureWorks, both polymers disclosed above, would provide topsheets of nearly 100% bio-based content.

A further example of a topsheet that may be used comprises a surfactant treated nonwoven web comprising spunbond bicomponent fibers having a core of (PLA), and a sheath comprising PLA. For example, in one embodiment, the core may comprise a PLA having a lower % D isomer of polylactic acid than that of the % D isomer PLA polymer used in the sheath. The PLA polymer with lower % D isomer will show higher degree of stress induced crystallization during spinning while the PLA polymer with higher D % isomer will retain a more amorphous state during spinning. The more amorphous sheath will promote bonding while the core showing a higher degree of crystallization will provide strength to the fiber and thus to the final bonded web. In one particular embodiment, the Nature Works PLA Grade PLA 6752 with 4% D Isomer can be used as the sheath while NatureWorks Grade 6202 with 2% D Isomer can be used as the core.

A further example of a nonwoven fabric that could be used as a topsheet in accordance with embodiments of this invention may include thermobonded carded webs comprised of cotton and polypropylene. Depending on the fibers employed such webs may or may not require addition of surfactants (as described above) to achieve a desired hydrophilic nature for use as topsheet nonwovens. Examples of polypropylene staple fibers useful to form such fabrics are available from Fibervisions Corporation as Grade T-198. Examples of cotton fibers for use to form such nonwoven fabrics include fibers sold under the product name TRUECOTTON® available from TJ Beall Company, and fibers sold under the product name HIGH-Q ULTRA® available from Barnhardt Manufacturing Company.

Preferably, the topsheet has a basis weight from about 8 to about 25 grams per square meter, and more preferably from about 12 to 17 grains per square meter.

There are a number of manufacturing techniques which may be used to manufacture the topsheet. For example, the topsheet may be a nonwoven web of fibers. When the topsheet comprises a nonwoven web, the web may be spunbonded, carded, wet-laid, meltblown, hydroentangled, combinations of the above, or the like. A preferred topsheet comprises a spunbond nonwoven fabric in which the fibers are thermally bonded to each other to form a coherent web.

The backsheet is positioned adjacent to an opposite surface of the absorbent core and is preferably joined thereto by attachment mechanisms such as those well known in the art. Suitable attachment mechanisms are described with respect to joining the topsheet to the absorbent core. Alternatively, the attachment means may comprise heat bonds, pressure bonds, ultrasonic bonds, dynamic mechanical bonds, or any other suitable attachment means or combinations of these attachment mechanisms as are known in the art.

The backsheet is impervious to liquids (e.g., urine) and is preferably manufactured from a thin plastic film, although other flexible liquid impervious materials may also be used. As used herein, the term “flexible” refers to materials which are compliant and will readily conform to the general shape and contours of the human body. The backsheet prevents the exudates absorbed and contained in the absorbent core from wetting articles which contact the diaper such as bedsheets and undergarments. The backsheet may thus comprise a woven or nonwoven material, polymeric films such as thermoplastic films, or composite materials such as a film-coated nonwoven material. Preferably, the backsheet is a thermoplastic film comprising a high content of bio-based materials. The backsheet may have a thickness of from about 0.012 mm (0.5 mil) to about 0.051 mm (2.0 mils).

Material for the backsheet may include the bio-based polymers discussed previously. For example, bio-based polymers for use in the backsheet may include polymers directly produced from organisms, such as polyhydroxyalkanoates (e.g., poly(beta-hydroxyalkanoate), poly(3-hydroxybutyrate-co-3-hydroxyvalerate, NODAX™), and bacterial cellulose; polymers extracted from plants and biomass, such as polysaccharides and derivatives thereof (e.g., gums, cellulose, cellulose esters, chitin, chitosan, starch, chemically modified starch), proteins (e.g., zein, whey, gluten, collagen), lipids, lignins, and natural rubber; and current polymers derived from naturally sourced monomers and derivatives, such as bio-polyethylene, bio-polypropylene, polytrimethylene terephthalate, polylactic acid, NYLON 11, alkyd resins, succinic acid-based polyesters, and bio-polyethylene terephthalate.

In one embodiment the backsheet can be a film comprised of bio-based polymers as previously discussed. In one example the film may be comprised of low density polyethylene (LDPE) derived from sugar cane such as provided by grades SEB853 or SLL1118/21 available from Braskem S. A.

In one embodiment, the backsheet may comprise a laminate structure having a liquid impervious film layer that is joined to a nonwoven web. Suitable films may be prepared from the bio-based polymers as previously discussed. In one example, the film may comprise a sugar cane derived polyethylene polymer, such as a film grade LDPE polyethylene grade SEB853/72 or SPB681/59 recommended by Braskem S. A for lamination. Suitable films may also include additives such as CaCO3 to improve film breathability while still maintaining fluid barrier properties.

In one embodiment, nonwovens for use in a laminated backsheet may include bio-based nonwovens as discussed above in connection with the topsheet. In one embodiment, such nonwovens may have a basis weight from 8 to 25 g/m2. For backsheet lamination, such nonwovens will preferably be made without application of surfactants. For example, the nonwoven web may comprise spunbond bicomponent fibers in which the fibers have a sheath-core configuration where the sheath and/or the core can be comprised of such bio-based polymers as polyethylene from sugar cane, PLA from corn, or lignin recovered from wood pulp manufacture for paper.

In some embodiments, the backsheet layer may comprise a laminate structure having a bio-based film layer, such as those discussed previously, that is laminated to a fabric layer having a spunbond-meltblown-spunbond (SMS) structure. In such embodiments, the meltblown layer may typically have a basis weight ranging from 1 to 3 g/m2, and the spunbond layers will typically have a basis weight ranging from 8 to 25 g/m2. Suitable bio-based materials for the meltblown and spunbond layers are discussed above.

The size of the backsheet is generally dictated by the size of the absorbent core and the exact diaper design selected. For example, in some embodiments the backsheet has a modified hourglass shape extending beyond the absorbent core a minimum distance of at least about 1.3 cm to about 2.5 cm (about 0.5 to about 1.0 inch) around the entire diaper periphery.

When present, the absorbent core may comprise any material that is capable of absorbing fluids and exudates. Preferably, the absorbent core comprises at least 75% by weight of bio-based materials. In the past suitable materials for use as the absorbent core included pulp, such as cellulosic pulp, tissue layers, and fluff pulp. However the trend toward thin diapers has required the replacement of increasing pulp content with synthetic superabsorbent polymers such as superabsorbent polymers available from BASF sold under the trademark of HYSORB®. Use of increasing quantities of such superabsorbent polymer has significantly reduced the weight % content of sustainable content in current thin diapers sold in Western Europe and the USA.

A preferred embodiment of the diaper of this invention is comprised of superabsorbent polymers comprised of monomers of significant bio-based material content. Use of bio-based acrylic acid monomer is an example of a route to bio-based superabsorbent polymer that may be used in embodiments of the invention. Sugar from corn is converted to 3-hydroxypropionic acid (3-HP) which is then converted to glacial acrylic acid. The resulting bio-based glacial acrylic acid is used to make bio-based superabsorbent polymers in one embodiment, the absorbent core may comprise a bio-based superabsorbent polymer derived from glacial acrylic acid. Such bio-based superabsorbent polymers have been developed by BASF, Cargill, and Novozymes. A superabsorbent polymer comprising up to 90 weight % bio-based sourced polyacrylic acid is discussed in U.S. Patent Publication No. 2013/0274697.

The absorbent core may be manufactured in a wide variety of sizes and shapes (e.g., rectangular, hourglass, “T”-shaped, asymmetric, etc.). The configuration and construction of the absorbent core may also be varied (e.g., the absorbent core may have varying caliper zones, a hydrophilic gradient, a superabsorbent gradient, or lower average density and lower average basis weight acquisition zones; or may comprise one or more layers or structures). The total absorbent capacity of the absorbent core should, however, be compatible with the design loading and the intended use of the diaper. Further, the size and absorbent capacity of the absorbent core may be varied to accommodate wearers ranging from infants through adults.

In some embodiments, the absorbent core may include a fluid acquisition distribution system. This system may comprise an acquisition layer, which is placed adjacent to or in proximity of topsheet. The acquisition layer helps to distribute fluids along the absorbent core to help improve efficiency, and to reduce or prevent fluid leakage. When present, the acquisition layer may comprise a bio-based material based acquisition layer (AQL layer). In one embodiment, an AQLL may be made by carding a web comprised of a blend of 7 denier hollow PLA-Type 820 2 inch cut length staple fibers (Fiber Innovations Technology-Johnson City, Tenn.) plus 3 denier Solid PLA-Type 821 2 inch length staple fibers (Fiber Innovations Technology-Johnson City, Tenn.); treating the resulting web via a kiss roll with a suspension of cooked starch (Type STABITEX 65401 from Cargill); exposing the resulting web of fiber and starch to elevated temperature via a combination of hot air and contact to steam heated dryer cans to both cure and dry the web; and winding the resulting web into a roll and slitting the resulting roll into children rolls. The resulting AQL layer fabric may be comprised of nearly 100% bio-based material content.

In some embodiments, the distribution system may also include a distribution layer that is disposed underneath the acquisition layer. In some embodiments, the distribution layer may be a core cover or core wrap that covers or surrounds the absorbent material of the absorbent core to prevent particles of the absorbent core from contacting the baby's skin. The function of typical core wrap is discussed in U.S. Pat. No. 5,458,592. Preferably, the core wrap permits fluid to pass into the absorbent core while maintaining containment of the absorbent material. In one embodiment, materials for the core wrap may comprise a fabric layer comprising a spunbond fabric, spunbond-meltblown fabric (SM), or an SMS fabric. Suitable bio-based materials for the spunbond and meltblown layers of the core wrap are discussed above in connection with the topsheet.

One example of a core wrap comprising an SM fabric or SMS fabric comprises one or more spunbond nonwoven layers comprising bicomponent fibers having a polypropylene sheath and a PLA core, which is joined to a layer comprising polypropylene meltblown fibers.

Another example of a core wrap comprising an SMS fabric comprises a spunbond nonwoven layer comprising bicomponent fibers having a PLA sheath (e.g., Nature Works PLA Grade PLA 6752 with 4% D Isomer), and a PLA core (e.g. NatureWorks Grade 6202 with 2% D Isomer). In one embodiment, the meltblown layer of the SMS fabric may be comprised of a PLA meltblown fibers (e.g., NatureWorks PLA grade 6252).

In a third embodiment, the core wrap may comprise an SMS fabric in which the the spunbond nonwoven layers comprise biocomponent fibers comprising a polypropylene sheath, and a PLA core. Examples of suitable polypropylenes typically have a melt flow rate (MFR) between 20 to 40 g/10 min (measured in accordance with ASTM D1238 (190° C./2.16 kg)) such as for example provided by Total Petrochemicals and Refining USA, Inc of La Port, Tex., 77571 USA as grades M 3766 (metallocene polypropylene) and 3764 or 3866 (Zeigler Natta polypropylene). Suitable materials for the PLA core are available from NatureWorks, such as under the product name PLA Grade 6202.

In one embodiment, the meltblown layer for use in the SMS fabrics may comprise meltblown fibers comprising a blend of PLA and polypropylene that has been reclaimed from spunbond bicomponent fibers comprised of PP/PLA using the process taught in the international Application PCT/US 2015/012658, the contents of which are hereby incorporated by reference Such meltblown webs are generally compatible for bonding to the sheath of the above bicomponent spunbond layers to provide a high bio-based material content SMS core wrap.

Typically, the spunbond bicomponent webs for use in the core wrap, have a sheath/core ratio that may be from approximately 30/70 to 70/30. For the above examples total basis weigh of the resulting SMS may be between about 8 g/m2 and about 15 g/m2 with the meltblown content being approximately 10% of the weight, based on the total weight of the fabric.

In accordance with certain embodiments, for example, at least the PLA spunbond nonwoven fabric layer may comprise a three-dimensional geometric bonding pattern. In such embodiments, for instance, the bonding pattern may comprise at least one of a diamond pattern, a hexagonal dot pattern, an oval-elliptic pattern, a rod-shaped pattern, or any combination thereof.

EXAMPLES

The following examples are provided for illustrating one or more embodiments of the present invention and should not be construed as limiting the invention.

Nonwoven fabrics in accordance with the invention were prepared via a Reifenhaeuser Reicofil-3 line or Reicofil-4 line. Each of the examples were prepared using the setup described in Example 1 unless otherwise indicated. Moreover, unless otherwise indicated all percentages are weight percentages. The materials used in the examples are identified below.

Test Methods

Titer was calculated from microscopic measurement of fiber diameter and known polymer density per German textile method C-1570.

Basis Weight was determined generally following the German textile method CM-130 from the weight of 10 layers of fabric cut into 10×10 cm squares.

Tensile was determined in accordance with Method 10 DIN 53857 using a sample with 5 cm width, 100 mm gauge length, and cross-head speed of 200 mm/min. Tensile strengths were measured at peak.

Elongation was determined in accordance with Method 10 DIN 53857 using a sample with 5 cm width, 100 mm gauge length, and cross-head speed of 200 mm/min. Elongations were measured at peak.

Fabric Shrinkage was determined by cutting three samples taken across the web width of nominal dimensions of MD of 29.7 cm and CD of 21.0 cm; measuring the actual MD and CD width at three locations in the sheet; placing the sample in water heated to 60 C for 1 minute; and remeasuring the MD and CD dimensions at the above three locations. The average width measurement after exposure divided by the original measurement X 100% yielded the % Shrinkage. A low % shrinkage value suggests that the continuous fibers comprising PLA have been spun and drawn at sufficient speed to yield after bonding a high strength stable fabric.

Comparative Examples 1, 2, and 3

In Comparative Examples 1, 2 and 3 a 100% PLA bicomponent fabric was prepared on a Reicofil-4 beam. A press roll (R-4 press roll) was positioned on the collection surface downstream of where the filaments are deposited on the collection surface. An Ionis Elektrostatik Discharging Electrode E3412 (i.e. ionization bar) was positioned above and extending over the collection surface in the cross direction and placed approximately 1 to 3 inches above the collection surface and 2 to 3 inches downstream of the R-4 press roll.

The fabrics were bicomponent 30/70 NatureWorks Grade 6752/NatureWorks Grade 6202/sheath/core made with ionization bars positioned as discussed above to minimize static. The fabrics of Comparative Examples 1, 2 and 3 were produced at spin beam temperatures of 235° C. at the extruder and 240° C. at the die. The fabric of Comparative Example 1 was produced at a fiber draw speed of 3600 m/min and a line speed of 145 m/min. The calender for Comparative Example 1 had calender temperatures of 160° C. for the pattern roll and 147° C. for the anvil roll and a calender pressure of 40 N/mm.

The fabric of Comparative Example 2 was produced using a fiber draw speed of 3800 m/min and a line speed of 90 m/min. The calender for Comparative Example 2 had calender temperatures of 160° C. for the pattern roll and 147° C. for the anvil roll and a calender pressure of 40 N/mm.

The fabric of Comparative Example 3 was produced using a fiber draw speed of 3200 m/min and a line speed of 145 m/min. The calender for Comparative Example 3 had calender temperatures of 160° C. for the pattern roll and 147° C. for the anvil roll and a calender pressure of 40 N/mm. Mechanical properties of Comparative Examples 1, 2, and 3 are summarized in Tables 4 and 5 below.

Inventive Example 1

In Inventive Example 1, a 100% PLA bicomponent fabric having a sheath/core structure was prepared in which 2 weight percent of a masterbatch comprising a PLA resin and a secondary alkane sulfonate was added to the polymer component defining the sheath. The setup of the system is the same as described above for Comparative Examples 1, 2, and 3.

The fabric was a bicomponent 30/70 NatureWorks Grade 6752/NatureWorks Grade 6202/sheath/core made with ionization bars as discussed above to minimize static. At the sheath extruder, 2% by weight of a masterbatch of Sukano Antistatic Product S 546 was combined with NatureWorks Grade 6752 to provide the sheath of the bicomponent fibers. BICO. The fabric of Inventive Example 1 was produced at spin beam temperatures of 235° C. at the extruder and 240° C. at the die. The fabric of Inventive Example 1 was produced at a fiber draw speed of 3800 m/min and a line speed of 145 m/min. The calender for Inventive Example 1 had calender temperatures of 160° C. for the pattern roll and 147° C. for the anvil roll and a calender pressure of 40 N/mm. Properties of Inventive Example 1 are summarized in Tables 4 and 5 below.

Inventive Example 2

In Inventive Example 2, a 100% PLA bicomponent fabric having a sheath/core arrangement was prepared in which 3 weight percent of a masterbatch comprising a PLA resin and a secondary alkane sulfonate was added to the polymer component defining the sheath. The setup of the system is the same as described above for Comparative Examples 1, 2, and 3.

The fabric was a bicomponent 30/70 NatureWorks Grade 6752/NatureWorks Grade 6202/sheath/core made with ionization bars as discussed above to minimize static. At the sheath extruder, 3% by weight of a masterbatch of Sukano Antistatic Product S 546 was combined with NatureWorks Grade 6752 to provide the sheath of BICO Example 12. The fabric of Inventive Example 2 was produced at spin beam temperatures of 235° C. at the extruder and 240° C. at the die. The fabric of Inventive Example 2 was produced at a fiber draw speed of 3550 m/min and a line speed of 145 m/min. The calender for Inventive Example 2 had calender temperatures of 160° C. for the pattern roll and 147° C. for the anvil roll and a calender pressure of 40 N/mm. Properties of Inventive Example 2 are summarized in Tables 4 and 5 below.

Inventive Example 3

In Inventive Example 3, a 100% PLA bicomponent fabric having a sheath/core arrangement was prepared in which 2 weight percent of a masterbatch comprising a PLA resin and a secondary alkane sulfonate was added to the polymer component defining the sheath. The setup of the system is the same as described above for Comparative Examples 1, 2, and 3.

The fabric was bicomponent 30/70 NatureWorks Grade 6752/NatureWorks Grade 6202/sheath/core made with ionization bars as discussed above to minimize static. At the sheath extruder, 2% by weight of a masterbatch of Sukano Antistatic Product S 546 was combined with NatureWorks Grade 6752 to provide the sheath of the fabric. The fabric was produced at spin beam temperatures of 235° C. at the extruder and 240° C. at the die. The fabric was produced at a fiber draw speed of 3400 m/min and a line speed of 90 m/min. The calender for Inventive Example 3 had calender temperatures of 160° C. for the pattern roll and 147° C. for the anvil roll and a calender pressure of 40 N/mm. Properties of Inventive Example 3 are summarized in Tables 4 and 5 below.

Inventive Example 4

In Inventive Example 4, a 100% PLA bicomponent fabric having a sheath/core arrangement was prepared in which 2 weight percent of a masterbatch comprising a PLA resin and a secondary alkane sulfonate was added to the polymer component defining the sheath. The setup of the system is the same as described above for Comparative Examples 1, 2, and 3.

The fabric was a bicomponent 30/70 NatureWorks Grade 6752/NatureWorks Grade 6202/sheath/core made with ionization bars as discussed above to minimize static. At the sheath extruder, 2% by weight of a masterbatch of Sukano Antistatic Product S 546 was combined with NatureWorks Grade 6752 to provide the sheath of bicomponent fabric. The fabric of Inventive Example 4 was produced at spin beam temperatures of 235° C. at the extruder and 240° C. at the die. The fabric of Inventive Example 4 was produced at a fiber draw speed of approximately 3400 m/min and a line speed of 241 m/min to yield a calculated basis weight of 15 grams/square meter. The calender for Inventive Example 4 had calender temperatures of 160° C. for the pattern roll and 147° C. for the anvil roll and a calender pressure of 40 N/mm. The mechanical properties of Inventive Example 14 were not evaluated.

TABLE 4 Nonwoven Mechanical Properties MD CD Tensile Tensile MD CD Basis MD per Basis CD per Basis MD % CD % Toughness Toughness Titer Weight Tensile Weight Tensile Weight Elong. Elong. Index Index Units N-m2/ N-m2/ Example DTEX g/m2 N/5 cm g-5 cm N/5 cm g-5 cm % % N-% N-% Comparative 1.8 23.8 35.1 1.47 13.0 0.546 13.3 24.03 467 312 Example 1 Comparative 1.7 39.8 70.7 1.78 26.6 0.668 14.7 28.61 1881 761 Example 2 Comparative 2.0 24.3 38.4 1.58 14.8 0.609 15.6 26.30 599 389 Example 3 Inventive 1.7 27.6 83.2 3.01 29.0 1.051 28.3 44.28 2355 1284 Example 1 Inventive 1.8 27.6 85.2 3.09 29.0 1.051 29.4 49.44 2505 1434 Example 2 Inventive 1.9 51.3 142.2 2.77 73.8 1.435 40.8 46.54 5802 3435 Example 3 Inventive — 15.0* — — — — — — — — Example 4 *Calculated basis weight for sample produced.

TABLE 5 Properties Normalized for Basis Weights. MD CD Fabric Root Tensile Tensile MD CD MD Relative CD Relative mean Square per Basis per Basis Toughness Toughness Toughness Toughness Toughness Basis Weight Weight Index Index Index per Index per index per Example Weight N-m2/ N-m2/ (MDTI) (CDTI) Basis Weight Basis Weight Basis Weight* Units g/m2 g-5 cm g-5 cm N-% N-% N-%/g/m2 N-%/g/m2 N-%/g/m2 Comparative 23.8 1.47 0.546 467 312 19.62 13.11 16.69 Example 1 Comparative 39.8 1.78 0.668 1881 761 47.26 19.12 36.05 Example 2 Comparative 24.3 1.58 0.609 599 389 24.65 16.01 20.78 Example 3 Inventive 27.6 3.01 1.051 2355 1284 85.32 46.52 68.12 Example 1 Inventive 27.6 3.09 1.051 2505 1434 90.76 51.96 73.95 Example 2 Inventive 51.3 2.77 1.435 5802 3435 113.1 66.96 92.94 Example 3 * Root ⁢ Mean ⁢ Square = ( MDTI ) 2 + ( CDTI ) 2 2 ; Fabric ⁢ Root ⁢ mean ⁢ Square ⁢ Toughness ⁢ Index ⁢ Per ⁢ Basis ⁢ Weight = ( ( MDTI ) 2 + ( CDTI ) 2 2 ) / Basis ⁢ weight

TABLE 6 Percent Increase in MD and CD Relative Index in Toughness Inventive Inventive Inventive Inventive Inventive Inventive Example 1 Example 2 Example 3 Example 1 Example 2 Example 3 (MD) (MD) (MD) (CD) (CD) (CD) Units Example (%) (%) (%) (%) (%) (%) Comparative 334.9 362.6 476.5 254.8 296.3 410.7 Example 1 Comparative 80.5 92.0 139.3 143.3 171.6 250.2 Example 2 Comparative 246.1 268.2 358.8 190.6 224.5 318.2 Example 3 Percent Increase: (ending value − starting value)/starting value × 100

TABLE 7 Shrinkage Resistance for PLA Spunbond Fabric Shrink Shrink Area (MD) (CD) Shrink Example % % % Comparative 3.1 −1.1 2.1 Example 1 Comparative 3.1 −1.4 1.8 Example 2 Comparative 2.9 −1.5 1.4 Example 3 Inventive 7.8 −0.9 7.0 Example 1 Inventive 6.4 −2.5 4.0 Example 2 Inventive 2.2 −3.3 −1.0 Example 3

From Tables 4 and 5 above, it can be seen that the inventive nonwoven fabrics exhibit significant improvements in mechanical properties in comparison to the identically prepared nonwoven fabrics that do not include the secondary alkane sulfonate. In this regard, the results provided in Table 5 are particularly telling. In Table 5, the results have been normalized to account for the differences in basis weights. Based on this data, it can be seen that the inventive nonwoven fabrics exhibited an increase in tensile strengths of greater than 50%/in comparison to the comparative examples. For example, the inventive nonwoven fabrics exhibited an increase in NMD tensile strength ranging from 55.6% (comparison of Inventive Example 3 and Comparative Example 2) to 110.2% (comparison of Inventive Example 2 and Comparative Example 1). For CD tensile strength, the inventive nonwoven fabrics exhibited an increase in CD tensile strength ranging from 57.3% (comparison of Inventive Example 1 and Comparative Example 2) to 162.8% (comparison of Inventive Example 3 and Comparative Example 1).

The inventive nonwoven fabrics also exhibited significant increases in toughness in comparison to the nonwoven fabrics of the comparative examples. Table 5 below shows both MD and CD Relative Index of Toughness (normalized for basis weight) for Comparative Examples 1-3 and Invention Examples 1-3. For example, the inventive nonwoven fabrics exhibited an increase in MD Relative Index of Toughness ranging from 80.5% (comparison of Inventive Example 1 and Comparative Example 2) to 476% (comparison of Inventive Example 3 and Comparative Example 1). For the CD Relative Index of Toughness, the inventive nonwoven fabrics exhibited an increase in CD Relative Index of Toughness ranging from 143% (comparison of Inventive Example 1 and Comparative Example 2) to 411% (comparison of Inventive Example 3 and Comparative Example 1).

When comparing properties of different nonwovens it is often useful to compare the root mean square of the combined values of the MD and CD property of interest. This method allows comparison of single values. The root mean square provides a single number that combines input from both the MD and the CD values by taking the square root of the sum of the square of the MD value plus the square of the CD value. Use of the root mean square method to combine the MD and the CD results is particularly useful if samples to be compared were made on different machines or under some different condition that might influence the MD/CD ratio. Table 5 below shows the root mean square of the Toughness Index per basis weight for the Comparative Samples 1-3 as well as the Invention samples 1-3. The Root Mean Square Toughness Index values normalized for basis weight show the comparative samples grouped between 10 and 40 N-%/g/m2. In contrast, the inventive nonwoven fabrics exhibited Root Mean Square Toughness Index values above 65 N-%/g/m2, and in particular, within a range of 55 to 100 N-%/g/m2. Thus, a very clear separation in the root mean square of the normalized Index of Toughness values can be seen for fabrics of the invention and the comparative samples.

To further evaluate the basis for the increases in tensile strengths, elongation, and toughness of the inventive nonwoven fabrics, SEM images of the fabric surfaces of Comparative Example 1 and Inventive Example 1 were obtained. FIGS. 1A and 1B are SEM images of Comparative Example 1 taken at a magnification of 250× and 100×, respectively. FIGS. 2A and 2B are SEM images of Inventive Example 1 taken at a magnification of 250× and 100×, respectively. The images were obtained with a PERSONAL SEM 75, available from RJ Lee Instruments Ltd., and a DESK V Sputterer, available from Denton Vacuum. As the SEM images were made at low magnification, 100× and 250×, sputtering with gold was not required. 5 mm×5 mm samples of each fabric were obtained and placed with in the SEM instrument. A low vacuum was obtained, and then the images were captured.

Surprisingly, a significant difference in bonding between the fibers was observed. In particular, the bond points of the fabric of Comparative Example 1 showed that the individual fibers were loosely bonded together, and that there was minimal polymer flow bonding adjacent fibers to each other. In comparison, the bond points of the fabric of Inventive Example 1, showed significant melting and flowing of the polymer of the individual fibers. Thus, the inventive fabric exhibited significant improvements in bonding in comparison to the comparative fabric that did not include the secondary alkane sulfonate.

In the following examples, the effect of the carrier resin for the secondary alkane sulfonate on the physical properties was explored. As explained below, the improvements in mechanical properties in the fabrics were shown to be due primarily to the presence of the secondary alkane sulfonate, and not to the presence of a lower molecular weight carrier resin in the masterbatch.

Comparative Example 4

In Comparative Example 4, a 100% PLA bicomponent fabric having a sheath/core arrangement was prepared in which 0.5% weight percent of NatureWorks Grade 6302 was added to the polymer component defining the sheath. NatureWorks Grade 6302 is commonly used as the carrier polymer for masterbatches added to PLA polymer formulations. It is therefore believed that this PLA resin provides a good approximation of the PLA resin in the secondary alkane sulfonate. The setup of the system is the same as described above for Comparative Examples 1, 2, and 3.

The fabric was a bicomponent 30/70 NatureWorks Grade 6752/NatureWorks Grade 6202/sheath/core made with ionization bars as discussed above to minimize static. At the sheath extruder, 0.5% weight percent of NatureWorks Grade 6302 2% by weight was combined with NatureWorks Grade 6752 to provide the sheath of bicomponent fabric. The fabric of Comparative Example 4 was made at processing conditions similar to those used for Inventive Examples 1-4, with the exceptions as shown in Table 8 below and the line speed was adjusted to provide a final basis weight of 25 GSM. Properties of Comparative Example 4 are summarized below in Table 9, below.

Comparative Example 5

In Comparative Example 5 a 100% PLA bicomponent fabric having a sheath/core arrangement was prepared in which 1.0% weight percent of NatureWorks Grade 6302 was added to the polymer component defining the sheath. The setup of the system is the same as described above for Comparative Examples 1, 2, and 3.

The fabric was a bicomponent 30/70 NatureWorks Grade 6752/NatureWorks Grade 6202/sheath/core made with ionization bars as discussed above to minimize static. At the sheath extruder, 1.0% weight percent of NatureWorks Grade 6302 2% by weight was combined with NatureWorks Grade 6752 to provide the sheath of bicomponent fabric. The fabric of Comparative Sample 4 was made at processing conditions similar to those used for Inventive Examples 1-4 except as shown in Table 8, below, and the line speed was adjusted to provide a final basis weight of 25 GSM. Properties of Comparative Example 5 are summarized below in Table 9.

Comparative Example 6

In Comparative Example 6 a 100% PLA bicomponent fabric having a sheath/core arrangement was prepared in which 2.0% weight percent of NatureWorks Grade 6302 was added to the polymer component defining the sheath. The setup of the system is the same as described above for Comparative Examples 1, 2, and 3.

The fabric was a bicomponent 30/70 NatureWorks Grade 6752/NatureWorks Grade 6202/sheath/core made with ionization bars as discussed above to minimize static. At the sheath extruder, 2.0% weight percent of NatureWorks Grade 6302 2% by weight was combined with NatureWorks Grade 6752 to provide the sheath of bicomponent fabric. The fabric of Comparative Example 6 was made at processing conditions similar to those used for Inventive Examples 1-4 except as shown in Table 8, below, and the line speed was adjusted to provide a final basis weight of 25 GSM. Properties of Comparative Example 6 are summarized below in 9, below.

Comparative Example 7

In Comparative Example 7 a 100% PLA bicomponent fabric having a sheath/core arrangement was prepared in which 3.5% weight percent of NatureWorks Grade 6302 was added to the polymer component defining the sheath. The setup of the system is the same as described above for Comparative Examples 1, 2, and 3.

The fabric was a bicomponent 30/70 NatureWorks Grade 6752/NatureWorks Grade 6202/sheath/core made with ionization bars as discussed above to minimize static. At the sheath extruder, 3.5% weight percent of NatureWorks Grade 6302 2% by weight was combined with NatureWorks Grade 6752 to provide the sheath of bicomponent fabric. The fabric of Comparative Sample 7 was made at processing conditions similar to those used for Examples of this invention 1-4 except as shown in Table 8, below, and the line speed was adjusted to provide a final basis weight of 25 GSM. Properties of Comparative Sample 7 are summarized below in Table 9, below.

Inventive Example 5

In Inventive Example 5, a 100% PLA bicomponent fabric having a sheath/core arrangement was prepared in which 0.3 weight percent of a masterbatch comprising a PLA resin and a secondary alkane sulfonate was added to the polymer component defining the sheath. The setup of the system is the same as described above for Comparative Examples 1, 2, and 3.

The fabric was a bicomponent 50/50 NatureWorks Grade 6752/NatureWorks Grade 6202/sheath/core made with ionization bars as discussed above to minimize static. At the sheath extruder, 0.3% by weight of a masterbatch of Sukano Product S 546 was combined with NatureWorks Grade 6752 to provide the sheath of bicomponent fabric. The fabric of Inventive Example 5 was produced was made at processing conditions similar to those used for Inventive Examples 1-4 except as shown in Table 8, below, and the line speed was adjusted to provide a final basis weight of 28 GSM. Properties of Inventive Example 5 are summarized below in Table 9, below.

Inventive Example 6

In Inventive Example 5, a 100% PLA bicomponent fabric having a sheath/core arrangement was prepared in which 0.3 weight percent of a masterbatch comprising a PLA resin and a secondary alkane sulfonate was added to the polymer component defining the sheath. The setup of the system is the same as described above for Inventive Examples 1, 2, and 3.

The fabric was a bicomponent 50/50 NatureWorks Grade 6752/NatureWorks Grade 6202/sheath/core made with ionization bars as discussed above to minimize static. At the sheath extruder, 0.3% by weight of a masterbatch of Sukano Product S 546 was combined with NatureWorks Grade 6752 to provide the sheath of bicomponent fabric. The fabric of Inventive Example 6 was produced was made at processing conditions similar to those used for Inventive Examples 1-4 except as shown in Table 8 below, and the line speed was adjusted to provide a final basis weight of 23 GSM. Properties of Inventive Example 6 are summarized below in Table 9, below.

TABLE 8 Process Conditions for Comparative Examples 4-7 and Inventive Examples 5-6 Calender Temperature Through- Cabin (Embossed/ Calender Example Put Pressure Smooth) Pressure Gap Units Kg/hr Pa C/C N/mm Setting Comparative 230 6000 165/140 40 22/26 Example 4 Comparative 230 6000 165/140 40 22/26 Example 5 Comparative 230 6000 165/140 40 22/26 Example 6 Comparative 230 6000 165/140 40 22/26 Example 7 Inventive 240 6500 152/142 40 20/24 Example 5 Inventive 240 6500 152/142 40 20/24 Example 6

TABLE 9 Mechanical Properties MD CD MD CD MD CD Toughness Toughness Basis MD Tensile per CD Tensile per MD % CD % Toughness Toughness Index per Index per Titer Weight Tensile Basis Weight Tensile Basis Weight Elong. Elong. Index Index BW BW Units N-m2/ N-m2/ Example DTEX g/m2 N/5 cm g-5 cm N/5 cm g-5 cm % % N-% N-% N-%/gsm N-%/gsm Comparative 1.8  23.12 38.97 1.69 13.85 0.599 14.75 25.33 574.81 477.47 24.86 20.65 Example 4 Comparative No Data 28.37 35.33 1.24 12.59 0.444 13.17 24.39 465.30 307.07 16.40 10.82 Example 5 Comparative No Data 22.62 34.87 1.54 12.15 0.537 13.21 24.56 460.63 298.40 20.36 13.19 Example 6 Comparative No Data 23.38 34.24 1.46 12.94 0.553 12.58 26.79 430.74 346.67 18.42 14.83 Example 7 Inventive 2.40 28.37 69.48 2.45 20.96 0.739 23.64 32.32 1642.51 677.43 57.90 23.88 Example 5 Inventive 2.07 23.12 52.93 2.89 15.43 0.667 25.18 32.79 1332.78 505.95 57.65 21.88 Example 6

There was no visible difference in the bonding sites for nonwovens fabrics above (Comparative Examples 4-7) made with PLA 6302 used as an additive versus nonwovens above made using addition of the masterbatch of Sukano Product 546 (Inventivw Examples 5 and 6). However, as from the mechanical data summarized in Table 9, a significant difference between the Comparative Examples and Inventive Examples 5 and 6 was observed. In particular, the examples including secondary alkane sulfonate exhibited significant improvements in MD and CD tensile strength, MD and CD elongation, and MD and CD Toughness Index in comparison to the comparative examples that only include the masterbatch PLA resin, but no secondary alkane sulfonate. Accordingly, it can be seen that the improvement in properties are attributed to the presence of the secondary alkane sulfonate, and not to the lower molecular weight PLA resin of the masterbatch.

It was also observed that during the manufacture of the fabrics, the fabrics of Inventive Examples 5 and 6 were more stable during calender bonding calender in comparison to the fabrics of Comparative Examples 4-7.

In the following examples, the hydrophilic nature of the PLA fabrics, and the effects of the secondary alkane sulfonate on the hydrophilicity of the fabrics were investigated. Inventive Examples 7-12 were prepared in accordance with the fabric of Inventive Fabrics 6 and 7. In each example, the amount of Sukano additive added to the sheath was varied and the effects on liquid Run-Off and Strike-through was evaluated at different time periods. The results are summarized in Tables 10 and 11, below.

Run-Off data was measured in accordance with the procedures set forth in WSP 80.9, and Strikethrough data as measured by test method WSP 70.3.

Runoff data measures the percent of a specified volume of fluid that runs off a fabric/absorbent combination that is supported at a specified angle from vertical. The fabric being evaluated is positioned overlying an absorbent material. During the test procedure, a fluid runs down the fabric and may, or may not, be absorbed into the absorbent material placed under the fabric being tested. If the fabric is hydrophobic a very high % of the fluid runs down and off the fabric/absorbent combination into a container for collection. If the fabric is very hydrophilic nearly all of the liquid is absorbed by the fabric/absorbent combination and the % Run-off is nearly equal to zero. The Runoff test is commonly repeated on the same piece of fabric three times. This procedure simulates multiple voids by the baby or adult into the diaper. Most typical commercial topsheets show a very low % run-off in the first insult. However the Run-off values commonly increases in the second and third insults as the surfactant is washed off and transported into the absorbent material under the test fabric. Thus, all hydrophilic surfactant may be lost following a first voiding. As a result, repeated voidings by a wearer, such as a baby, may result in loss of hydrophilicity of the fabric, which may undesirably lead to leakage of the diaper.

Strike Through data measures the time for a specified volume of liquid applied at downward at a 90 degree angle to the a test fabric surface that is backed by an absorbent layer. The strike though values after one or multiple insults can be measured. A low strike through value suggests that liquid will rapidly penetrate the hydrophilic treated fabric and be absorbed by the absorbent material simulated the core of the diaper. Results after multiple strike through tests provide an indication of the permanence of the surfactant treatment. Increasing values of strikethrough with multiple insults suggests that the surfactant is being washed into the underlying absorbent material, such as an absorbent core, with risk that the diaper topsheet will become hydrophobic and the diaper will leak. An optimized topsheet will provide strikethrough values of 4 seconds or less even after up to three insults.

TABLE 10 Run-Off Test Results % Run-Off % Run-Off % Run Off % Run Off % Run Off Tested Tested Tested Tested Tested % Run Off % Run Off % Run Off Sukano Fresh 24 Hours 14 days 14 days 14 days 30 days 30 days 30 days Additive as Made after Made after Made after Made after Made after Made after Made after Made Example Level % First Gush First Gush First Gush Second Gush Third Gush First Gush Second Gush Third Gush Example 7 0.25%  98.6 99.5 96.36 96.16 96.92 98.85 92.20 86.48 Example 8 0.5% 98.3 98.8 95.88 96.08 95.36 98.97 98.20 98.99 Example 9 1.0% 98.4 97.6 — — — 98.01 6.87 2.15 Example 10  .,5% 98.4 98.3 — — — 97.15 0.00 0.11 Example 11  2% 98.0 97.7 — — — 95.79 0.00 0.00 Example 12 2.5% 93.0 89.4 — — — 72.91 0.00 0.00

TABLE 11 Strike-through Test Results Strike - Strike - Strike - Strike - Strike - Through Through Through Through Through Strike - Strike - Strike - (Sec.) (Sec.) (Sec.) (Sec.) (Sec.) Through Through Through Tested Tested Tested Tested Tested (Sec.) (Sec.) (Sec.) Sukano Fresh 24 Hours 14 days 14 days 14 days 30 days 30 days 30 days Additive as Made after Made after Made after Made after Made after Made after Made after Made Example Level % First Gush First Gush First Gush Second Gush Third Gush First Gush Second Gush Third Gush Example 7 0.25%  8.2 9.3 4.95 4.86 4.43 8.34 5.43 5.03 Example 8 0.5% 8.6 8.4 6.09 4.42 3.58 4.65 3.70 3.28 Example 9 1.0% 9.6 8.6 — — — 5.15 1.95 2.30 Example 10 1.5% 5.9 5.5 — — — 4.08 1.90 2.38 Example 11  2% 4.4 4.3 — — — 3.35 1.90 2.16 Example 12 2.5% 2.9 3.4 — — — 1.88 2.00 2.18

The % Run-Off and Strike-Through Data in Tables 10 and 11 surprisingly demonstrated that not only does the secondary alkane sulfonate improve the mechanical properties of the PLA fabric, but it also modifies the liquid transport properties of the fabrics.

In addition, the results demonstrate that the Run-Off and Strike-through are dependent, at least in part, on the level of the secondary alkane sulfonate as well as age of the fabric. For example, at two weeks 100% PLA fabric containing 0.25% and 0.5% of the additive exhibited hydrophobic properties as measured by both runoff and strikethrough. After a month following production, the fabrics containing 0.25% and 0.5% of the additive still exhibited hydrophobic properties. However, at higher additive levels a response is observed suggestive of decreasing hydrophobicity. Surprising and unexpected, the response is opposite to that seen with typical surfactant treated topsheet. Initial runoff and strikethrough suggests a hydrophobic fabric. However, following the second and third insults, the fabric exhibits hydrophilic properties.

This effect suggests that fabrics in accordance with the invention may be prepared that provide hydrophilic properties following multiple voids. In particular, fabrics for use as a topsheet may be prepared in which the fabric is treated with a low add-on surfactant to provide initial hydrophilicity, but then takes advantage of the additive to provide a wash-off resistant hydrophilicity after multiple insults. Such a topsheet may be of particular interest for use in overnight diapers and incontinent products.

Non-Limiting Exemplary Embodiments

Having described various aspects and embodiments of the invention herein, further specific embodiments of the invention include those set forth in the following paragraphs.

Certain embodiments according to the invention are directed to a spunbond nonwoven fabric comprising a plurality of fibers that are bonded to each other to form a coherent web, wherein the fibers comprise a blend of a polylactic acid (PLA) and at least one secondary alkane sulfonate. In some embodiments, the blend is present at a surface of the plurality of fibers. In one embodiment, the at least one secondary alkane sulfonate comprises an alkane chain having from C10-C18, and wherein at least one of the secondary carbons of the alkane chain includes a sulfonate moiety. For example, the at least one secondary alkane sulfonate has one of the following structures:

wherein m+n is a number between 7 and 16, and X is independently a C1-C4 alkyl or absent. In some embodiments, the at least one secondary alkane sulfonate has the following structure:

wherein m+n is a number between 8 and 15, and in particular, wherein m+n is a number between 11 and 14. In some embodiments, the at least one secondary alkane sulfonate comprises a salt of sodium or potassium.

In certain embodiments, the at least one secondary alkane sulfonate is present in an amount ranging from about 0.0125 to 2.5 weight percent, based on the total weight of the fiber. For example, the fiber may have a sheath/core bicomponent arrangement in which the blend is present in the sheath, and wherein the secondary alkane sulfonate is present in the sheath in an amount ranging from about 0.1 to 0.75 weight percent, based on the total weight of the sheath. In another embodiment, the fiber may have a sheath/core bicomponent arrangement in which the blend is present in the sheath, and wherein the secondary alkane sulfonate is present in the sheath in an amount ranging from about 0.2 to 0.6 weight percent, based on the total weight of the sheath. In yet another embodiment, the fiber has a sheath/core bicomponent arrangement in which the blend is present in the sheath, and wherein the secondary alkane sulfonate is present in the sheath in an amount ranging from about 0.3 to 0.4 weight percent, based on the total weight of the sheath.

In one embodiment, the plurality of fibers comprise bicomponent fibers. In some embodiments, the plurality of fibers comprise bicomponent fibers and the at least one secondary alkane sulfonate is present in only one of the component of the fibers. In one embodiment, the bicomponent fibers have a sheath/core configuration and the sheath comprises a blend of the PLA and the at least one secondary alkane sulfonate. In some embodiments, the core comprises PLA and does not include the at least one secondary alkane sulfonate. In still other embodiments, the bicomponent fibers comprise a side-by-side arrangement.

In one embodiment, the core comprises at least one of a polyolefin, a polyester, a PLA, or any combination thereof. In a preferred embodiment, each of the sheath and the core comprises PLA. In certain embodiments, the sheath comprises a first PLA grade, the core comprises a second PLA grade, and the first PLA grade and the second PLA grade are different.

In some embodiments, the fabric exhibits an increase in tensile strength in at least one of the machine direction or cross direction in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate. For example, the fabric may exhibit an increase in tensile strength in at least one of the machine direction or cross direction of at least 50% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits an increase in tensile strength in at least one of the machine direction or cross direction that is from 50% to 200% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits an increase in machine direction tensile strength that is from about 50 to 150% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits an increase in machine direction tensile strength that is from about 55 to 125% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits an increase in machine direction tensile strength that is from about 65 to 110% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits an increase in machine direction tensile strength that is from about 65 to 110% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits an increase in machine direction tensile strength that is from about 85 to 110% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits an increase in machine direction tensile strength that is from about 90 to 110% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits an increase in cross direction tensile strength that is from about 50 to 200% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits an increase in cross direction tensile strength that is from about 50 to 170% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits an increase in cross direction tensile strength that is from about 55 to 165% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits an increase in cross direction tensile strength that is from about 65 to 160% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits an increase in cross direction tensile strength that is from about 85 to 150% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits an increase in cross direction tensile strength that is from about 90 to 125% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits an increase in elongation in at least one of the machine direction or cross direction in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits a machine direction Index of Toughness that is from about 2,000 to 7,500 N-%.

In one embodiment, the fabric exhibits a machine direction Index of Toughness that is from about 2,300 to 6,500 N-%.

In one embodiment, the fabric exhibits a machine direction Index of Toughness that is from about 2,300 to 6,000 N-%.

In one embodiment, the fabric exhibits a cross direction Index of Toughness that is from about 1,000 to 5,000 N-%.

In one embodiment, the fabric exhibits a cross direction Index of Toughness that is from about 1,250 to 5,000 N-%.

In one embodiment, the fabric exhibits a cross direction Index of Toughness that is from about 1,250 to 3,500 N-%.

In one embodiment, the fabric exhibits an increase in machine direction Index of Toughness that is from about 20 to 1,250% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits an increase in machine direction Index of Toughness that is at least 100% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits an increase in cross direction Index of Toughness that is from about 50 to 1,000% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits an increase in cross direction Index of Toughness that is at least 85% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In some embodiments, the fabric exhibits a machine direction Relative Index of Toughness that is from about 50 to 150 N-%/g/m2, such as a machine direction Relative Index of Toughness that is from about 75 to 125 N-%/g/m2, and in particular, a machine direction Relative Index of Toughness that is from about 85 to 115 N-%/g/m2. In one embodiment, the fabric exhibits a cross direction Relative Index of Toughness that is from about 40 to 100 N-%/g/m2, such as a cross direction Relative Index of Toughness that is from about 45 to 85 N-%/g/m2.

In certain embodiments, the fabric exhibits an increase in machine direction Relative Index of Toughness that is from about 100 to 1,000% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate, such as an increase in machine direction Relative Index of Toughness that is from 80 to 500% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

In one embodiment, the fabric exhibits an increase in cross direction Relative Index of Toughness that is at least 100% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate, such as an increase in cross direction Relative Index of Toughness that is from about 140 to 410% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

Additional aspects of the invention are directed to a spunbond nonwoven fabric comprising a plurality of fibers that are bonded to each other to form a coherent web, wherein the fibers comprise from 95 to 100% polylactic acid (PLA), and wherein the fibers exhibit a root mean square of a Toughness Index per basis weight having a value that is at least 55 N-%/g/m2. In one such embodiment, the root mean square of the Toughness Index per basis weight is a value that is greater than 65 N-%/g/m2, such as a value from about from about 65 to 150 N-%/g/m2. In one embodiment, the fibers of the fabric comprise less than 5 weight % of additives.

Aspects of the invention are also directed to absorbent articles comprising a nonwoven fabric having fibers comprising a blend of a PLA resin and at least one secondary alkane sulfonate. Examples of absorbent articles include diapers and femine sanitary pads.

Additional aspects of the invention are directed to a process for preparing a polylactic acid (PLA) spunbond nonwoven fabric, the process comprising: blending a PLA resin and at least one secondary alkane sulfonate, under heat and pressure, to form a stream of molten or semi-molten PLA resin; forming a plurality of PLA continuous filaments from said stream; depositing the plurality of PLA continuous filaments onto a collection surface; exposing the plurality of PLA continuous filaments to ions; and bonding the plurality of PLA continuous filaments to form the PLA spunbond nonwoven fabric, wherein the continuous filaments comprise a blend of PLA and the at least one secondary alkane sulfonate.

In one embodiment, the filaments comprise a blend of PLA and the at least on secondary alkane sulfonate. The filaments may be monocomponent or bicomponent. In a preferred embodiment, the filaments have a sheath/core bicomponent configuration in which the sheath comprises the blend of the PLA and the at least one secondary alkane sulfonate. In some embodiments, the core may comprise PLA or a synthetic polymer, such as a polyolefin or a polyester. Preferably, the core comprises PLA.

Advantageously, the process may be performed at relatively high draw speeds. For example, the continuous filaments may be drawn at a fiber draw speed greater than about 2500 m/min., such as a fiber draw speed from about 3000 m/min to about 5500 m/min., or a fiber draw speed from about 3000 m/min to about 4000 m/min.

In one embodiment, the step of exposing the plurality of PLA continuous filaments to ions comprising passing the filaments in close proximity to an ionization source, such as an ionization bar. In one embodiment, the ionization source comprises an ionization bar that is positioned above the collection surface, and in the cross direction of the fabric.

In one embodiment, the step of bonding the continuous filaments to form the PLA spunbond nonwoven fabric comprises thermal point bonding the web with heat and pressure via a calender having a pair of cooperating rolls including a patterned roll. In some embodiments, the thermal point bonding the continuous filaments comprises imparting a three-dimensional geometric bonding pattern onto the PLA spunbond nonwoven fabric.

In one embodiment, the bonding of the pattern onto the PLA spunbond nonwoven fabric comprises imparting at least one of a diamond pattern, a hexagonal dot pattern, an oval-elliptic pattern, a rod-shaped pattern, or any combination thereof onto the PLA spunbond nonwoven fabric. In some embodiments, the bonding pattern covers from about 5% to about 30% of the surface area of the patterned roll. For example, the bonding pattern may cover from about 10% to about 25% of the surface area of the patterned roll.

In one embodiment, the process additionally comprises dissipating static charge from the PLA spunbond nonwoven fabric proximate to the calender via a first static control unit. In one embodiment, the static control unit comprises a second ionization source, such as an ionization bar. For instance, the second ionization source may comprise an ionization bar extending over at least one of the plurality of PLA continuous filaments or the PLA spunbond nonwoven fabric in a cross direction.

In one embodiment, dissipating static charge from the PLA spunbond nonwoven fabric comprises contacting the PLA spunbond nonwoven fabric with a static bar.

In some embodiments, the process may further comprise cutting the PLA spunbond nonwoven fabric to form cut PLA spunbond nonwoven fabric; exposing the cut PLA spunbond nonwoven fabric to ions via a third ionization source; and winding the cut PLA spunbond nonwoven fabric into rolls. In one embodiment, the third ionization source comprises an ionization bar extending over at least one of the plurality of PLA continuous filaments or the PLA spunbond nonwoven fabric in a cross direction.

Additional aspects of the invention are directed to a system for preparing a polylactic acid (PLA) spunbond nonwoven fabric, the system comprising: a first PLA source and a source of a secondary alkane sulfonate, configured to provide a stream comprising molten or semi-molten PLA resin and the secondary alkane sulfonate; a spin beam in fluid communication with the first PLA source, the spin beam configured to extrude and draw a plurality of PLA continuous filaments, wherein the PLA continuous filaments comprise a blend of the PLA and the secondary alkane sulfonate; a collection surface disposed below an outlet of the spin beam onto which the PLA continuous filaments are deposited to form the PLA spunbond nonwoven fabric; a first ionization source positioned and arranged to expose the PLA continuous filaments to ions; and a calender positioned downstream of the first ionization source.

In one embodiment, the first ionization source is positioned above the collection surface and downstream of a point at where the PLA continuous filaments are deposited on the collection surface. In another embodiment, the first ionization source is positioned between the outlet of the spin beam and the collection surface. Preferably, the first ionization source and the collection surface are separated by a distance from about 1 inch to about 24 inches, such as a distance from about 1 inch to about 12 inches, and in particular, a distance from about 1 inch to about 5 inches.

In some embodiments, the system may further comprise a static control unit positioned and arranged to dissipate static from the PLA spunbond nonwoven fabric proximate to the calender. In one embodiment, the static control unit comprises a passive static bar, or a second ionization source, or a combination thereof.

In one embodiment, the system includes a press roll positioned downstream from the outlet of the spin beam. In some embodiments, the system may comprise a vacuum source disposed below the collection surface.

In certain embodiments, the system may include a winder positioned downstream from the calender; and a third ionization source positioned and arranged to expose the PLA spunbond nonwoven fabric to ions proximate to the winder.

In one embodiment, the at least one of the first ionization source, the static control source, and the third ionization source each comprise an ionization bar extending over at least one of the plurality of PLA continuous filaments or the PLA spunbond nonwoven fabric in a cross direction. In one embodiment, the first ionization source, the static control source, and the third ionization source are configured to actively dissipate static charge created during preparation of the PLA spunbond nonwoven fabric.

In one embodiment, the first ionization source is positioned downstream from the press roll. In some embodiments, the first ionization source is positioned between the spin beam and the press roll. When present, the static control unit may be positioned upstream from, and adjacent to, the calender. In other embodiments, the static control unit is positioned downstream from, and adjacent to, the calender.

In one embodiment, the calender comprises a pair of cooperating rolls including a patterned roll, the patterned roll comprising a three-dimensional geometric bonding pattern. In some embodiments, the bonding pattern comprises at least one of a diamond pattern, a hexagonal dot pattern, an oval-elliptic pattern, a rod-shaped pattern, or any combination thereof. In one embodiment, the bonding pattern covers from about 5% to about 30% of the surface area of the patterned roll, such as from about 10% to about 25% of the surface area of the patterned roll.

In one embodiment, the system is configured to produce a nonwoven fabric of continuous filaments having a bicomponent arrangement. In one embodiment, the continuous filaments have a sheath/core arrangement. In a preferred embodiment, the system is configured to produce filaments in which the blend of the PLA and the secondary alkane sulfonate defines the sheath. In some embodiments, the core comprises a PLA resin. The PLA resin may be the same or different than that of the sheath. In one embodiment, the core is free of the secondary alkane sulfonate.

In some embodiments, the secondary alkane sulfonate is present in an amount ranging from about 0.0125 to 2.5 weight percent, based on the total weight of the fiber. In one embodiment, the continuous filaments have a sheath/core bicomponent arrangement in which the blend is present in the sheath, and wherein the secondary alkane sulfonate is present in the sheath in an amount ranging from about 0.1 to 0.75 weight percent, based on the total weight of the sheath.

In one particular embodiment, the system is configured to prepare continuous filaments having a sheath/core bicomponent in which the blend is present in the sheath, and wherein the secondary alkane sulfonate is present in the sheath in an amount ranging from about 0.2 to 0.6 weight percent, based on the total weight of the sheath. In other embodiments, the system is configured to produce continuous filaments having a sheath/core bicomponent arrangement in which the blend is present in the sheath, and wherein the secondary alkane sulfonate is present in the sheath in an amount ranging from about 0.3 to 0.4 weight percent, based on the total weight of the sheath.

Modifications of the invention set forth herein will come to mind to one skilled in the art to which the invention pertains having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the invention is not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims

1. A nonwoven fabric comprising a plurality of fibers that are bonded to each other to form a coherent web, wherein the fibers comprise a polymeric blend of a biobased aliphatic polyester and a secondary alkane sulfonate, wherein the amount of secondary alkane sulfonate in the polymeric blend is from about 0.0125 to 2.5 weight percent, based on the total weight of the blend, and wherein the nonwoven fabric exhibits a machine direction Index of Toughness that is from about 2,000 to 7,500 N-%.

2. The nonwoven fabric according to claim 1, the fabric exhibits an increase in cross direction Index of Toughness that is from about 50 to 1,000% in comparison to an identical fabric that does not include the secondary alkane sulfonate.

3. The nonwoven fabric according to claim 1, wherein the fabric exhibits an increase in cross direction Index of Toughness that is at least 85% in comparison to an identical fabric that does not include the secondary alkane sulfonate.

4. The nonwoven fabric according to claim 1, wherein the fabric exhibits an increase in machine direction Relative Index of Toughness that is from about 100 to 1,000% in comparison to an identical fabric that does not include the secondary alkane sulfonate.

5. The nonwoven fabric according to claim 1, wherein the fabric exhibits an increase in machine direction Relative Index of Toughness that is from 80 to 500% in comparison to an identical fabric that does not include the secondary alkane sulfonate.

6. The nonwoven fabric according to claim 1, wherein the fabric exhibits a root mean square of the Toughness Index per basis weight is a value that is greater than 65 N-%/g/m2, such as a value from about from about 65 to 150 N-%/g/m2.

7. The nonwoven fabric according to claim 1, wherein the fabric exhibits a machine direction Index of Toughness that is from about 2,300 to 6,000 N-%.

8. The nonwoven fabric according to claim 1, wherein the fabric exhibits a cross direction Index of Toughness that is from about 1,000 to 5,000 N-%.

9. The nonwoven fabric according to claim 1, wherein the fabric exhibits a cross direction Index of Toughness that is from about 1,250 to 5,000 N-%.

10. The nonwoven fabric according to claim 1, wherein the fabric exhibits a cross direction Index of Toughness that is from about 1,250 to 3,500 N-%.

11. The nonwoven fabric according to claim 1, wherein the fabric exhibits an increase in tensile strength in at least one of the machine direction or cross direction that is from 50% to 200% in comparison to an identical fabric that does not include the secondary alkane sulfonate.

12. The nonwoven fabric according to claim 1, wherein the fabric exhibits an increase in machine direction tensile strength that is from about 50 to 150% in comparison to an identical fabric that does not include the secondary alkane sulfonate.

13. The nonwoven fabric according to claim 1, wherein the fabric exhibits an increase in machine direction tensile strength that is from about 55 to 125% in comparison to an identical fabric that does not include the secondary alkane sulfonate.

14. The nonwoven fabric according to claim 1, wherein the fabric exhibits an increase in cross direction tensile strength that is from about 50 to 200% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

15. The nonwoven fabric according to claim 1, wherein the fabric exhibits an increase in cross direction tensile strength that is from about 85 to 150% in comparison to an identical fabric that does not include the at least one secondary alkane sulfonate.

16. The nonwoven fabric according to claim 1, wherein the polymeric blend is hydrophilic.

17. The nonwoven fabric according to claim 1, wherein the polymeric blend is hydrophobic.

18. The fabric of claim 1, wherein the plurality of fibers are bonded via calender bonding or air through bonding.

19. An absorbent article comprising the fabric of claim 1.

20. A spunbond nonwoven fabric comprising a polarity of filaments comprised of a bio-based polymer and wherein the filaments are air through bonded.

21. A process for preparing a nonwoven fabric, the process comprising:

blending a biobased aliphatic polyester and a secondary alkane sulfonate, under heat and pressure, to form a stream of molten or semi-molten resin comprised of a blend of the biobased aliphatic polyester and the secondary alkane sulfonate;
forming a plurality of filaments from said stream;
depositing the plurality of filaments onto a collection surface;
exposing the deposited plurality of filaments to ions provided by a first ionization source;
and
bonding the plurality of filaments to form the nonwoven fabric.

22. The process of claim 21, wherein the amount of secondary alkane sulfonate in the blend is from about 0.0125 to 2.5 weight percent, based on the total weight of the blend.

Patent History
Publication number: 20230279591
Type: Application
Filed: May 12, 2023
Publication Date: Sep 7, 2023
Applicants: Fitesa Germany GmbH (Peine), Fitesa Simpsonville, Inc. (Simpsonville, SC)
Inventors: Elena Novarino (Hannover), Gary Drews (Greenville, SC), Jason Hamilton (Peine), Stephen Chester (Simpsonville, SC), Alfredo Izzo (Peine), David D. Newkirk (Greer, SC)
Application Number: 18/196,794
Classifications
International Classification: D04H 3/009 (20060101); D04H 3/011 (20060101); D01F 8/14 (20060101); D01F 1/10 (20060101); D01F 6/62 (20060101); D04H 3/147 (20060101); A61F 13/15 (20060101); A61F 13/51 (20060101); D01D 5/38 (20060101); D01D 7/00 (20060101); D04H 3/16 (20060101);