EP1217107B1 - Elektrospinnverfahren zur Herstellung von Stärkefilamenten für flexible Strukturen - Google Patents

Elektrospinnverfahren zur Herstellung von Stärkefilamenten für flexible Strukturen Download PDF

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Publication number
EP1217107B1
EP1217107B1 EP00127813A EP00127813A EP1217107B1 EP 1217107 B1 EP1217107 B1 EP 1217107B1 EP 00127813 A EP00127813 A EP 00127813A EP 00127813 A EP00127813 A EP 00127813A EP 1217107 B1 EP1217107 B1 EP 1217107B1
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EP
European Patent Office
Prior art keywords
starch
filaments
molding member
weight
process according
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EP00127813A
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English (en)
French (fr)
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EP1217107A1 (de
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to NZ508818A priority Critical patent/NZ508818A/xx
Priority to ZA200007425A priority patent/ZA200007425B/xx
Priority to AU72219/00A priority patent/AU760124B2/en
Priority to NO20006375A priority patent/NO20006375L/no
Priority to SG200007497A priority patent/SG93288A1/en
Priority to AT00127813T priority patent/ATE294882T1/de
Priority to SK1963-2000A priority patent/SK19632000A3/sk
Priority to ES00127813T priority patent/ES2241543T3/es
Priority to CZ20004785A priority patent/CZ20004785A3/cs
Priority to EP00127813A priority patent/EP1217107B1/de
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to RU2000131894/04A priority patent/RU2201945C2/ru
Priority to DE60019944T priority patent/DE60019944T2/de
Priority to JP2000387783A priority patent/JP3598313B2/ja
Priority to CA002329289A priority patent/CA2329289C/en
Publication of EP1217107A1 publication Critical patent/EP1217107A1/de
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Publication of EP1217107B1 publication Critical patent/EP1217107B1/de
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
    • D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21F—PAPER-MAKING MACHINES; METHODS OF PRODUCING PAPER THEREON
    • D21F11/00—Processes for making continuous lengths of paper, or of cardboard, or of wet web for fibre board production, on paper-making machines
    • D21F11/006—Making patterned paper

Definitions

  • the present invention relates to flexible structures comprising starch filaments, and more specifically, to flexible structures having differential regions.
  • Cellulosic fibrous webs such as paper are well known in the art. Low density fibrous webs are in common use today for paper towels, toilet tissue, facial tissue, napkins, wet wipes, and the like. The large demand for such paper products has created a demand for improved versions of the products and the methods of their manufacture. In order to meet such demands, papermaking manufacturers must balance the costs of machinery and resources with the total cost of delivering the products to the consumer.
  • wood cellulosic fibers are re-pulped, beaten or refined to achieve a level of fiber hydration in order to form an aqueous pulp slurry.
  • Processes for the making of paper products for use in tissue, toweling, and sanitary products generally involve the preparation of the aqueous slurry and then subsequently removing the water from the slurry while contemporaneously rearranging the fibers therein to form a paper web. Subsequent to dewatering, the web is processed into a dry roll or sheet form and eventually converted into a consumer package.
  • Various types of machinery must be employed to assist in the dewatering process and converting operations requiring a significant investment in capital.
  • additives such as strength resins, debonding surfactants, softening agents, pigments, lattices, synthetic micro-spheres, fire-retardants, dyes, perfumes, etc.
  • additives such as strength resins, debonding surfactants, softening agents, pigments, lattices, synthetic micro-spheres, fire-retardants, dyes, perfumes, etc.
  • the efficient retention of these additives at the wet end of a papermaking process presents difficulty to the manufacturer since that portion which is not retained creates not only an economic loss but also significant pollution problems if it becomes part of a plant effluent.
  • Additives can also be added to the paper web subsequent to dewatering via coating or saturation processes commonly known in the art. These processes usually require that excess heating energy be consumed to re-dry the paper after coating.
  • the coating systems are required to be solvent based which increases capital costs and requires recovery of volatile materials to meet regulatory requirements.
  • the present invention provides a flexible structure comprising long starch filaments and a process for making same, which process comprises the steps
  • the present invention provides a flexible structure comprising a plurality of starch filaments, wherein the structure comprises two or more regions having distinct intensive properties for improved strength, absorbency, and softness.
  • the present invention also provides methods of making starch filaments.
  • the process for making continuous starch filaments comprises the steps of:
  • a flexible structure comprises a plurality of starch filaments. At least some of the plurality of starch filaments have a size from about 0.001 dtex to 135 dtex, and more specifically from 0,01dtex to 5 dtex.
  • An aspect ratio of a length of a major axis of at least some starch filaments to an equivalent diameter of a cross-section perpendicular to the major axis of the starch filaments is greater than 100/1, more specifically greater than 500/1, and still more specifically greater than 1000/1, and even more specifically, greater than 5000/1.
  • the structure comprises at least a first region and a second region, each of the first and second regions having at least one common intensive property selected from the group consisting of density, basis weight, elevation, opacity, crepe frequency, and any combination thereof. At least one common intensive property of the first region differs in value from the at least one common intensive property of the second region.
  • one of the first and second regions comprises a substantially continuous network, and the other of the first and second regions comprises a plurality of discrete areas dispersed throughout the substantially continuous network. In another embodiment, at least one of the first region and the second region comprises a semi-continuous network.
  • the flexible structure can further comprise at least a third region having at least one intensive property that is common with and differs in value from the intensive property of the first region and the intensive property of the second region.
  • at least one of the first, second, and third regions can comprise a substantially continuous network.
  • at least one of the first, second, and third regions can comprise discrete, or discontinuous, areas.
  • at least one of the first, second, and third regions can comprise substantially semi-continuous areas.
  • at least one of the first, second, and third regions can comprise a plurality of discrete areas dispersed throughout the substantially continuous network.
  • the substantially continuous network region can have a relatively high density relative to a relatively low density of the plurality of discrete areas.
  • the first region defines a first elevation
  • the second region outwardly extends from the first region to define a second elevation greater (relative to the horizontal reference plane) than the first elevation.
  • the first region can define a first elevation
  • the second region can define a second elevation
  • the third region can define a third elevation when the structure is disposed on a horizontal reference plane.
  • At least one of the first, second, and third elevations can be different from at least one of the other elevations, for example, the second elevation can be intermediate the first elevation and the third elevation.
  • the second region comprises a plurality of starch pillows, wherein an individual pillow can comprise a dome portion extending from the first elevation to the second elevation and a cantilever portion laterally extending from the dome portion at the second elevation.
  • a density of the starch cantilever portion can be equal to or different from at least one of a density of the first region and a density of the dome portion, or be intermediate the density of the first region and the density of the dome portion.
  • the cantilever portions are typically elevated from the first plane to form substantially void spaces between the first region and the cantilever portions.
  • the flexible structure is made by producing the plurality of starch filaments by electro-spinning; providing a molding member having a three-dimensional filament-receiving side structured to receive the plurality of starch filaments thereon, depositing the plurality of starch filaments to the filament-receiving side of the molding member, wherein the plurality of starch filaments at least partially conform to the pattern thereof; and separating the plurality of the starch filaments from the molding member.
  • the step of depositing the plurality of starch filaments to the filament-receiving side of the molding member may include causing the plurality of starch filaments to at least partially conform to the three-dimensional pattern of the molding member. That can be accomplished by for example, applying a fluid pressure differential to the plurality of starch filaments.
  • the step of depositing the plurality of starch filaments to the molding member comprises depositing the starch filaments at an acute angle relative to the filament-receiving side of the molding member, wherein the acute angle is from about 5 degrees to about 85 degrees.
  • the molding member comprises, in one embodiment, a resinous framework joined to a reinforcing element.
  • the molding member can be fluid-permeable, fluid-impermeable, or partially fluid-permeable.
  • the reinforcing element can be positioned between the filament-receiving side and at least a portion of the backside of the framework.
  • the filament-receiving side can comprise a substantially continuous pattern, a substantially semi-continuous pattern, a discontinuous pattern, or any combination thereon.
  • the framework can comprise a plurality of apertures therethrough that can be continuous, discrete, or semi-continuous, analogously and conversely to the pattern of the framework.
  • the molding member is formed by a reinforcing element disposed at a first elevation, and a resinous framework joined to the reinforcing element in a face-to-face relationship and outwardly extending from the reinforcing element to form a second elevation.
  • the molding member can comprise a plurality of interwoven yarns, a felt, or any combination thereof.
  • the plurality of the starch filaments When the plurality of the starch filaments is deposited to the filament-receiving side of the molding member, they tend, due to their flexibility and/or as a result of application of fluid pressure differential, to at least partially conform to the three-dimensional pattern of the molding member, thereby forming the first regions of the plurality of starch filaments supported by the patterned framework, and the second regions of the plurality of starch filaments deflected into the aperture or apertures thereof and supported by the reinforcing element.
  • the molding member comprises suspended portions.
  • the resinous framework of such a molding member comprises a plurality of bases outwardly extending from the reinforcing element and a plurality of cantilever portions laterally extending from the bases at the second elevation to form void spaces between the cantilever portions and the reinforcing element, wherein the plurality of bases and the plurality of cantilever portions form, in combination, the three-dimensional filament-receiving side of the molding member.
  • Such a molding member can be formed by at least two layers joined together in a face-to-face relationship such that portions of the framework of one of the layers correspond to apertures in the other layer.
  • the molding member comprising suspended portions can also be formed by differential curing of the photosensitive resinous layer through a mask having a pattern comprising areas of differential opacity.
  • the process of making the flexible structure of the present invention may further comprise a step of densifying selected portions of the plurality of starch filaments, for example, by applying a mechanical pressure to the plurality of starch filaments.
  • the process may further include a step of foreshortening the plurality of starch filaments.
  • the foreshortening may be accomplished by creping, microcontraction, or a combination thereof.
  • An electro-spinning process for making starch filaments comprises steps of providing a starch composition having an extensional viscosity from about 50 pascal•second to about 20,000 pascal•second; and electro-spinning the starch composition, thereby producing starch filaments having a size from about 0.001 dtex to about 135 dtex.
  • the step of electro-spinning the starch composition typically comprises electro-spinning the starch composition through a die.
  • the starch in the starch composition has a weight-average molecular weight from about 1,000 to about 2,000,000; and the starch composition has a capillary number of at least 0.05, and more specifically at least 1.00. In one embodiment, the starch composition comprises from about 20% to about 99% by weight is amylopectin.
  • the starch in the starch composition may have a weight-average molecular weight from about 1,000 to about 2,000,000.
  • the starch composition may comprise a high polymer having a weight-average molecular weight of at least 500,000.
  • the starch composition may comprise from about 10% to about 80% by weight of the starch and from about 20% to about 90% by weight of additives.
  • Such a starch composition may have an extensional viscosity from about 100 Pascal•seconds to about 15,000 Pascal•seconds at a temperature from about 20 °C to about 180°C.
  • the starch composition may comprise from about 20% to about 70% by weight of the starch and from about 30% to about 80% by weight of additives. Such a starch composition may have the extensional viscosity from about 200 Pascal•seconds to about 10,000 Pascal•seconds at a temperature from about 20 °C to about 100°C.
  • the starch composition have the extensional viscosity from about 200 Pascal•seconds to about 10,000 Pascal•seconds may have a capillary number from about 3 to about 50. More specifically, the starch composition having the extensional viscosity from about 300 pascal•seconds to about 5,000 pascal•seconds may have a capillary number from about 5 to about 30.
  • the starch composition comprises from about 0.0005% to about 5% by weight of a high polymer substantially compatible with the starch and having an average molecular weight of at least 500,000.
  • the starch composition can comprise an additive selected from the group consisting of plasticizers and diluents.
  • a starch composition may further comprise from about 5% to about 95% by weight of a protein, wherein the protein comprises a corn-derived protein, a soybean-derived protein, a wheat derived protein, or any combination thereof.
  • the process for making the starch filaments may further comprise a step of attenuating the starch filaments with streams of air.
  • the present invention does also provide a process for making a flexible structure comprising starch filaments, the process comprising steps of:
  • “Flexible structure comprising starch filaments,” or simply “flexible structure,” is an arrangement comprising a plurality of starch filaments that are mechanically inter-entangled to form a sheet-like product having certain predetermined microscopic geometric, physical, and aesthetic properties.
  • Starch filament is a slender, thin, and highly flexible object comprising starch and having a major axis which is very long, compared to the fiber's two mutually-orthogonal axes that are perpendicular to the major axis.
  • An aspect ratio of the major's axis length to an equivalent diameter of the filament's cross-section perpendicular to the major axis is greater than 100/1, more specifically greater than 500/1, and still more specifically greater than 1000/1, and even more specifically, greater than 5000/1.
  • the starch filaments may comprise other matter, such as, for example water, plasticizers, and other optional additives.
  • Equivalent diameter is used herein to define a cross-sectional area and a surface area of an individual starch filament, without regard to the shape of the cross-sectional area.
  • S the starch filament's cross-sectional area (without regard to its geometrical shape)
  • ⁇ 3.14159
  • D the equivalent diameter.
  • this cross-sectional area can be expressed as a circular area having the equivalent diameter D.
  • Pseudo-thermoplastic in conjunction with “materials” or “compositions” is intended to denote materials and compositions that by the influence of elevated temperatures, dissolution in an appropriate solvent, or otherwise can be softened to such a degree that they can be brought into a flowable state, in which condition they can be shaped as desired, and more specifically, processed to form starch filaments suitable for forming a flexible structure.
  • Pseudo-thermoplastic materials may be formed, for example, under combined influence of heat and pressure.
  • Pseudo-thermoplastic materials differ from thermoplastic materials in that the softening or liquefying of the pseudo-thermoplastics is caused by softeners or solvents present, without which it would be impossible to bring them by any temperature or pressure into a soft or flowable condition necessary for shaping, since pseudo thermoplastics do not "melt” as such.
  • the influence of water content on the glass transition temperature and melting temperature of starch can be measured by differential scanning calorimetery as described by Zeleznak and Hoseny in "Cereal Chemistry", Vol. 64, No. 2, pp. 121-124, 1987.
  • Pseudo-thermoplastic melt is a pseudo-thermoplastic material in a flowable state.
  • Micro-geometry and permutations thereof refers to relatively small (i. e., “microscopical") details of the flexible structure, such as, for example, surface texture, without regard to the structure's overall configuration, as opposed to its overall (i. e., "macroscopical") geometry.
  • Terms containing "macroscopical” or “macroscopically” refer to an overall geometry of a structure, or a portion thereof, under consideration when it is placed in a two-dimensional configuration, such as the X-Y plane.
  • the flexible structure when it is disposed on a flat surface, comprises a relatively thin and flat sheet.
  • the structure can comprise a plurality of first regions that form a first plane having a first elevation, and a plurality of domes or "pillows" dispersed throughout and outwardly extending from the framework region to form a second elevation.
  • Intensive properties are properties which do not have a value dependent upon an aggregation of values within the plane of the flexible structure .
  • a common intensive property is an intensive property possessed by more than one region.
  • Such intensive properties of the flexible structure of the present invention include, without limitation, density, basis weight, elevation, opacity, and crepe frequency (if the structure is to be foreshortened). For example, if a density is a common intensive property of two differential regions, a value of the density in one region can differ from a value of the density in the other region. Regions (such as, for example, a first region and a second region) are identifiable areas distinguishable from one another by distinct intensive properties.
  • Basis weight is the weight (measured in grams force) of a unit area of the starch flexible structure , which unit area is taken in the plane of the starch filament structure. The size and shape of the unit area from which the basis weight is measured is dependent upon the relative and absolute sizes and shapes of the regions having differential basis weights.
  • Density is the ratio of the basis weight to a thickness (taken normal to the plane of the flexible structure) of a region.
  • Apparent density is the basis weight of the sample divided by the caliper with appropriate unit conversions incorporated therein. Apparent density used herein has the units of grams / centimeters cubed (g/cm 3 ).
  • Caliper is a macroscopic thickness of a sample measured as described below. Caliper should be distinguished from the elevation of differential regions, which is microscopical characteristic of the regions.
  • Glass transition temperature is the temperature at which the material changes from a viscous or rubbery condition to a hard and relatively brittle condition.
  • Machine direction is the direction parallel to the flow of the flexible structure being made through the manufacturing equipment.
  • Cross-machine direction is the direction perpendicular to the machine direction and parallel to the general plane of the flexible structure being made.
  • X,” “Y,” and “Z” designate a conventional system of Cartesian coordinates, wherein mutually perpendicular coordinates "X” and “Y” define a reference X-Y plane, and “Z” defines an orthogonal to the X-Y plane.
  • Z-direction designates any direction perpendicular to the X-Y plane.
  • Z-dimension means a dimension, distance, or parameter measured parallel to the Z-direction.
  • substantially continuous region refers to an area within which one can connect any two points by an uninterrupted line running entirely within that area throughout the line's length. That is, the substantially continuous region has a substantial "continuity" in all directions parallel to the first plane and is terminated only at edges of that region.
  • the term "substantially,” in conjunction with continuous, is intended to indicate that while an absolute continuity is preferred, minor deviations from the absolute continuity may be tolerable as long as those deviations do not appreciably affect the performance of the flexible structure (or a molding member) as designed and intended.
  • Substantially semi-continuous region refers an area which has "continuity" in all, but at least one, directions parallel to the first plane, and in which area one cannot connect any two points by an uninterrupted line running entirely within that area throughout the line's length.
  • the semi-continuous framework may have continuity only in one direction parallel to the first plane.
  • Discontinuous regions refer to discrete, and separated from one another areas that are discontinuous in all directions parallel to the first plane.
  • Absorbency is the ability of a material to take up fluids by various means including capillary, osmotic, solvent, or chemical action and retain such fluids. Absorbency can be measured according to the test described herein.
  • “Flexibility” is the ability of a material or structure to deform under a given load without being broken, regardless of the ability or inability of the material or structure to return itself to its pre-deformation shape.
  • Molding member is a structural element that can be used as a support for the starch filaments that can be deposited thereon during a process of making the flexible structure of the present invention, and as a forming unit to form (or “mold") a desired microscopical geometry of the flexible structure of the present invention.
  • the molding member may comprise any element that has the ability to impart a three-dimensional pattern to the structure being produced thereon, and includes, without limitation, a stationary plate, a belt, a woven fabric, and a band.
  • Reinforcing element is a desirable, but not necessary, element in some embodiments of the molding member, serving primarily to provide or facilitate integrity, stability, and durability of the molding member comprising, for example, a resinous material.
  • the reinforcing element can be fluid-permeable, fluid-impermeable, or partially fluid-permeable, and may comprise a plurality of interwoven yarns, a felt, a plastic, other suitable synthetic material, or any combination thereof.
  • Press-surface is a surface that can be pressed against the fillament-receiving side of the molding member having a plurality of starch filaments thereon, to deflect, at least partially, the starch filaments into the molding member having a three-dimensional pattern of depressions/protrusions therein.
  • Decitex or “dtex,” is a unit of measure for a starch filament expressed in grams per 10,000 meters, grams / 10,000 meters.
  • Melt-spinning is a process by which a thermoplastic or pseudo-thermoplastic material is turned into fibrous material through the use of an attenuation force. Melt-spinning can include mechanical elongation, melt-blowing, spun-bonding, and electro-spinning.
  • Mechanism elongation is the process inducing a force on a fiber thread by having it come into contact which a driven surface, such as a roll, to apply a force to the melt thereby making fibers.
  • Melt-blowing is a process for producing fibrous webs or articles directly from polymers or resins using high-velocity air or another appropriate force to attenuate the filaments.
  • the attenuation force is applied in the form of high speed air as the material exits the die or spinnerette.
  • spun-bonding comprises the process of allowing the fiber to drop a predetermined distance under the forces of flow and gravity and then applying a force via high velocity air or another appropriate source.
  • Electro-spinning is a process that uses electric potential as the force to attenuate the fibers.
  • Dry-spinning also commonly known as “solution-spinning,” involves the use of solvent drying to stabilize fiber formation. A material is dissolved in an appropriate solvent and is attenuated via mechanical elongation, melt-blowing, spun-bonding, and/or electro-spinning. The fiber becomes stable as the solvent is evaporated.
  • Weight-spinning comprises dissolving a material in a suitable solvent and forming small fibers via mechanical elongation, melt-blowing, spun-bonding, and/or electro-spinning. As the fiber is formed it is run into a coagulation system normally comprising a bath filled with an appropriate solution that solidifies the desired material, thereby producing stable fibers.
  • High Polymer substantially compatible with starch means that the high polymer is capable of forming a substantially homogeneous mixture composition with the starch (i.e., the composition that appears transparent or translucent to the naked eye) when the composition is heated to a temperature above the softening and/or its melting temperature.
  • “Melting temperature” means the temperature or the range of temperature at or above which the starch composition melts or softens sufficiently to be capable of being processed into starch filaments in accordance with the present invention. It is to be understood that some starch compositions are pseudo-thermoplastic compositions and as such may not exhibit pure “melting” behavior.
  • Processing temperature means the temperature of the starch composition, at which temperature the starch filaments of the present invention can be formed, for example, by attenuation.
  • a flexible structure 100 comprising pseudo-thermoplastic starch filaments comprises at least a first region 110 and a second region 120.
  • Each of the first and second regions has at least one common intensive property, such as, for example, a basis weight or density.
  • the common intensive property of the first region 110 differs in value from the common intensive property of the second region 120.
  • the density of the first region 110 can be higher than the density of the second region 120.
  • the first and second regions 110 and 120 of the flexible structure 100 of the present invention can also differentiate in their respective micro-geometry.
  • the first region 110 comprises a substantially continuous network forming a first plane at a first elevation when the structure 100 is disposed on a flat surface; and the second region 120 can comprise a plurality of discrete areas dispersed throughout the substantially continuous network. These discrete areas may, in some embodiments, comprise discrete protuberances, or "pillows,” outwardly extending from the network region to form a second elevation greater than the first elevation, relative to the first plane.
  • pillows can also comprise a substantially continuous pattern and a substantially semi-continuous pattern.
  • the substantially continuous network region can have a relatively high density, and the pillows have a relatively low density. In another embodiment, the substantially continuous network region can have a relatively low basis weight, and the pillows have a relatively high basis weight. In still other embodiments, the substantially continuous network region can have a relatively low density, and the pillows can have a relatively high density. An embodiment is contemplated, in which the substantially continuous network region can have a relatively high basis weight, and the pillows have a relatively low basis weight.
  • the second region 120 can comprise a semi-continuous network.
  • the second region 120 comprises discrete areas 122, similar to those shown in Fig. 1; and semi-continuous areas 121, extending in at least one direction as seen in the X-Y plane (i. e., a plane formed by the first region 110 of the structure 100 disposed on a flat surface).
  • the flexible structure 100 comprises a third region 130 having at least one intensive property that is common with and differs in value from the intensive property of the first region 110 and the intensive property of the second region 120.
  • the first region 110 can have the common intensive property having a first value
  • the second region 120 can have the common intensive property having a second value
  • the third region 130 can have the common intensive property having a third value, wherein the first value can be different from the second value, and the third value can be different from the second value and the first value.
  • the first region 110 defines the plane having the first elevation
  • the second region 120 extends therefrom to define the second elevation.
  • the third region 130 defines a third elevation, wherein at least one of the first, second, and third elevations is different from at least one of the other elevations.
  • the third elevation can be intermediate the first and second elevations.
  • Fig. 3 shows yet another embodiment of the flexible structure 100 of the present invention, in which embodiment the second region 120 comprises a plurality of starch pillows, wherein at least some of the pillows comprises a starch dome portion 128 and a starch cantilever portion 129 extending from the starch dome portion 128.
  • the starch cantilever portion 129 is elevated from the X-Y plane and extends, at an angle, from the dome portion 128, to form substantially void spaces, or "pockets,” 115 between the first region 110, the starch domes 128 extending therefrom, and the starch cantilever portions 129.
  • the flexible structure 100 schematically shown in Fig. 3 is believed to exhibit very high, for a given basis weight, absorbency characteristics.
  • the pockets 115 are characterized by having none or very little amount of starch filaments therein.
  • the term "substantially" void pockets 115 is intended to recognize that due to a highly flexible nature of the structure 100 and individual starch filaments comprising the structure 100, some insignificant amount of starch filaments or their portions may be found in the pockets 115.
  • a density of the pockets 115 is not greater than 0.005 gram per cubic centimeter (g/cc), more specifically, not greater than 0.004 g/cc, and still more specifically not greater than 0.003 g/cc.
  • the flexible structure 100 comprising the cantilever portions 129 is characterized by an enhanced overall surface area, relative to that of the comparable structure not having the cantilever portions 129.
  • an enhanced overall surface area relative to that of the comparable structure not having the cantilever portions 129.
  • the greater the absorption surface area of a structure the greater the absorption capacity thereof, all other parameters being equal.
  • the cantilever portions 129 may comprise third regions of the structure 100.
  • a density of the starch cantilever portions 129 is intermediate a density of the first region 110 and a density of the second region 120 comprising the dome portion(s).
  • the density of the dome portion 128 can be intermediate a relatively high density of the first region 110 and a relatively low density of the cantilever portion 129.
  • the basis weight of the cantilever portion 129 can be equal to, intermediate, or greater than one or both of the first region 110 and the dome portion 128.
  • Figs. 8 and 9 schematically show two embodiments of a process for making a flexible structure 100 comprising starch filaments.
  • starch filaments for the flexible structure 100 according to the present invention can be made by a variety of techniques known in the art.
  • the starch filaments can be produced from the pseudo-thermoplastic melt starch compositions by various melt-spinning processes. Sizes of the starch filaments may vary, from about 0.001 dtex to about 135 dtex, more specifically from about 0.005 dtex to about 50 dtex, and even more specifically from about 0.01 dtex to about 5.0 dtex.
  • U.S. Patent Nos. 5,516,815 and 5,316,578 to Buehler et al. relate to starch compositions for making starch filament using a melt-spinning process.
  • the melt starch composition can be extruded through a spinnerette to produce filaments having diameters slightly enlarged relative to the diameter of the die orifices of the spinnerette (i.e., due to a die swell effect).
  • the filaments are subsequently drawn down mechanically or thermomechanically by a drawing unit to reduce the fiber diameter.
  • an extruded starch composition can be forced through a spinneret (not shown) forming a vertically oriented curtain of downwardly-advancing starch filaments.
  • the starch filaments can be quenched with air in conjunction with a suction-type drawing or attenuating air slot.
  • U.S. Pat. No. 5,292,239 issued to Zeldin, et al., on March 8, 1994 discloses a device that reduces significant turbulence in the air flow in order to uniformly and consistently apply a drawing force to the starch filaments.
  • the disclosure of that patent is incorporated by reference herein for the limited purposes of teaching ways and equipment for reducing turbulence in the air flow when forming starch filaments.
  • starch filaments can be produced from a mixture comprising starch, water, plasticizers, and other optional additives.
  • the suitable starch mixture can be converted to a pseudo-thermoplastic melt in an extruder and conveyed through a spinneret to a drawing unit forming a vertically oriented curtain of downward advancing starch filaments.
  • the spinneret can comprise an assembly which is known in the art.
  • the spinneret can include a plurality of nozzle bores with holes having cross-sectional areas suitable for starch filament production.
  • the spinneret can be adapted to the fluidity of the starch composition so that every nozzle bore has the same rate of flow, if so desired. Alternatively, the rates of flow of differential nozzles can vary.
  • a drawing unit (not shown), can be located downstream of the extruder, and may comprise an open upper end, an open lower end opposite thereto, and an air supply manifold supplying compressed air to internal nozzles oriented in a downward direction. As compressed air flows through the internal nozzles, air is drawn into the open upper end of the drawing unit forming a rapidly moving stream of air flowing in the downward direction. The air stream produces a drawing force on the starch filaments causing them to be attenuated or stretched before exiting the open lower end of the drawing unit.
  • the starch filaments suitable for the flexible structure 100 can be produced by an electro-spinning process, wherein an electric field is applied to a starch solution to form charged starch jet.
  • the electro-spinning process is known in the art.
  • starch composition suitable for production of the starch filaments used in the flexible structure 100 of the present invention.
  • That starch composition comprises starch having a weight-average molecular weight ranging from about 1,000 to about 2,000,000, and can contain a high polymer that is substantially compatible with starch and has a weight-average molecular weight of at least 500,000. In one embodiment, that starch composition can have from about 20% to about 99% by weight of amylopectin. The disclosure of this commonly-assigned application is incorporated herein by reference.
  • a starch polymer can be mixed with water, plasticizers, and other additives, and a resulting melt can be processed (for example, extruded) and configured to produce starch filaments suitable for the flexible structure of the present invention.
  • the starch filaments may have from a trace amount to one hundred percent of starch, or be a blend of starch and other suitable materials, such as, for example, cellulose, synthetic materials, proteins, and any combination thereof.
  • Starch polymers can include any naturally occurring starch, physically modified starch or chemically modified starch. Suitable naturally occurring starches can include, without limitation, corn starch, potato starch, sweet potato starch, wheat starch, sago palm starch, tapioca starch, rice starch, soybean starch, arrow root starch, bracken starch, lotus starch, waxy maize starch, high amylose corn starch, and commercial amylose powder. Naturally occurring starches, particularly corn starch, potato starch, and wheat starch, are the starch polymers of choice due to their availability.
  • Physically modified starch is formed by changing its dimensional structure.
  • Physically modified starch can include ⁇ -starch, fractionated starch, moisture and heat treated starch and mechanically treated starch.
  • Chemically modified starch may be formed by reaction of its OH groups with alkylene oxides, and other ether-, ester-, urethane-, carbamate-, or isocyanate-forming substances. Hydroxyalkyl, acetyl, or carbamate starches or mixtures thereof are among embodiments of chemically modified starches.
  • the degree of substitution of the chemically modified starch is from 0.05 to 3.0, and more specifically from 0.05 to 0.2.
  • a native water content can be from about 5% to about 16% by weight, and more specifically, from about 8% to about 12%.
  • the amylose content of the starch is from 0% to about 80%, and more specifically, from about 20% to about 30%.
  • a plasticizer can be added to the starch polymer to lower the glass transition temperature of the starch filaments being made, thereby enhancing their flexibility.
  • the presence of the plasticizer can lower the melt viscosity which in turn facilitates the melt extrusion process.
  • the plasticizer is an organic compound having at least one hydroxyl group, such as, for example, a polyol. Sorbitol, mannitol, D-glucose, polyvinyl alcohol, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, sucrose, fructose, glycerol and mixtures thereof have been found suitable.
  • plasticizers include sorbitol, sucrose, and fructose in quantities ranging from about 0.1% by weight to about 70% by weight, more specifically from about 0.2% by weight to about 30% by weight, and still more specifically from about 0.5% by weight to about 10% by weight.
  • additives can be typically included with the starch polymer as a processing aid and to modify physical properties, such as, for example, elasticity, dry tensile strength, and wet strength, of the extruded starch filaments.
  • Additives are typically present in quantities ranging from 0.1% to 70% by weight on a non-volatiles basis (meaning that the quantity is calculated by excluding volatiles such as water).
  • the examples of additives include, without limitation, urea, urea derivatives, cross-linking agents, emulsifiers, surfactants, lubricants, proteins and their alkali salts, biodegradable synthetic polymers, waxes, low melting synthetic thermoplastic polymers, tackifying resins, extenders, and mixtures thereof.
  • biodegradable synthetic polymers include, without limitation, polycaprolactone, polyhydroxybutyrates, polyhydroxyvalerates, polylactides, and mixtures thereof.
  • Other additives include optical brighteners, antioxidants, flame retardants, dyes, pigments, and fillers.
  • an additive comprising urea in quantities ranging from 0.5% to 60% by weight can beneficially be included in the starch composition.
  • Suitable extenders for use herein include gelatin; vegetable proteins, such as corn protein, sunflower protein, soybean proteins, cotton seed proteins; and water soluble polysaccharides, such as alginates, carrageenans, guar gum, agar, gum arabic and related gums, and pectin; and water soluble derivatives of cellulose, such as alkylcelluloses, hydroxyalkylcelluloses, carboxymethylcellulose, etc.
  • water soluble synthetic polymers such as polyacrylic acids, polyacrylic acid esters, polyvinylacetates, polyvinylalcohols, polyvinylpyrrolidone, etc., may be used.
  • Lubricant compounds may further be added to improve flow properties of the starch material during the process of the present invention.
  • the lubricant compounds can include animal or vegetable fats, preferably in their hydrogenated form, especially those which are solid at room temperature. Additional lubricant materials include mono-glycerides and di-glycerides and phosphatides, especially lecithin.
  • a lubricant compound that includes mono-glyceride, glycerol mono-stearate is believed to be beneficial.
  • inorganic fillers such as the oxides of magnesium, aluminum, silicon, and titanium
  • inorganic salts including alkali metal salts, alkaline earth metal salts, phosphate salts, etc., may be used as processing aides.
  • Glyoxylated polyacrylamide resins have also been found to be of utility as wet strength resins. These resins are described in U.S. Patent Nos. 3,556,932, issued on January 19, 1971, to Coscia, et al. and 3,556,933, issued on January 19, 1971, to Williams et al..
  • One commercial source of glyoxylated polyacrylamide resins is Cytec Co. of Stanford, Connecticut, which markets one such resin under the mark ParezTM 631 NC.
  • Still other water-soluble cationic resins that can be used in this invention are urea formaldehyde and melamine formaldehyde resins.
  • the more common functional groups of these polyfunctional resins are nitrogen containing groups such as amino groups and methylol groups attached to nitrogen.
  • Polyethylenimine type resins may also find utility in the present invention.
  • temporary wet strength resins such as Caldas 10 (manufactured by Japan Carlit) and CoBond 1000 (manufactured by National Starch and Chemical Company) may be used in the present invention.
  • one cross-linking agent is the wet strength resin KymeneTM, in quantities ranging from about 0.1% by weight to about 10% by weight, and more specifically from about 0.1% by weight to about 3% by weight.
  • the starch compostion should exhibit certain rheological behavior during processing, such as a certain extensional viscosity and a certain capillary number.
  • rheological behavior such as a certain extensional viscosity and a certain capillary number.
  • the type of processing electro-spinning
  • Extensional, or elongational, viscosity ( ⁇ e ) relates to melt extensibility of the starch composition, and is particularly important for extensional processes such as starch filament making.
  • the extensional viscosity includes three types, depending on the type of deformation of the composition: uniaxial or simple extensional viscosity, biaxial extensional viscosity, and pure shear extensional viscosity.
  • the uniaxial extensional viscosity is especially important for uniaxial extensional processes such as mechanical elongation, melt-blowing, spun-bonding, and electro-spinning.
  • the other two extensional viscosities are important for the biaxial extension or forming processes for making films, foams, sheets or parts.
  • thermoplastics such as polyolefins, polyamides and polyesters
  • extensional viscosity and shear viscosity of these conventional thermoplastic materials and blends thereof. That is, the spinnability of the material can be determined simply by the melt shear viscosity, even though the spinnablity is a property controlled primarily by melt extensional viscosity.
  • the correlation is quite robust such that the fiber industry has relied on the melt shear viscosity in selecting and formulating melt spinnable materials.
  • the melt extensional viscosity has rarely been used as an industrial screening tool.
  • starch compositions of the present invention do not necessarily exhibit such a correlation between shear and extensional viscosities.
  • the starch compositions herein exhibit melt flow behavior typical of a non-Newtonian fluid and as such may exhibit a strain hardening behavior, that is, the extensional viscosity increases as the strain or deformation increases.
  • the shear viscosity of the composition remains relatively unchanged, or even decreases slightly.
  • a starch composition would be expected to exhibit decreased melt processability and would not be expected to be suitable for melt-extensional processes.
  • the starch composition herein shows a significant increase in extensional viscosity when even a small amount of high polymer is added. Consequently, the starch composition herein is found to have enhanced melt extensibility and is suitable for melt extensional processes, especially those including melt-blowing, spun-bonding, and electro-spinning.
  • Some starch compositions herein may have low melt viscosity such that they may be mixed, conveyed, or otherwise processed in traditional polymer processing equipment typically used for viscous fluids, such as a stationary mixer equipped with metering pump and spinneret.
  • the shear viscosity of the starch composition may be effectively modified by the molecular weight and molecular weight distribution of the starch, the molecular weight of the high polymer, and the amount of plasticizers and/or solvents used. It is believed that reducing the average molecular weight of the starch is an effective way to lower the shear viscosity of the composition.
  • the melt-processable starch compositions have an extensional viscosity in the range of from about 50 Pa•s to about 20,000 Pa•s, more specifically from about 100 Pa•s to about 15,000 Pa•s, more specifically from about 200 Pa•s to about 10,000 Pa•s, and even more specifically from about 300 Pa•s to about 5,000 Pa•s and yet more specifically from about 500 Pa•s to about 3,500 Pa•s at a certain temperature.
  • the extensional viscosity is calculated according to the method set forth hereinafter in the Analytical Methods section.
  • the amount and the type of polymeric components used can affect the rheological (including the extensional viscosity) behavior of the starch composition.
  • Such factors include, without limitation: the amount and the type of polymeric components used, the molecular weight and molecular weight distribution of the components, including the starch and the high polymers, the amylose content of the starch, the amount and type of additives (e.g., plasticizers, diluents, processing aids), the type of processing (e. g., melt-blowing or electro-spinning) and the processing conditions, such as temperature, pressure, rate of deformation, and relative humidity, and in the case of non-Newtonian materials, the deformation history (i.e., a time or strain history dependence).
  • Some materials can strain-harden, i.
  • the presence and properties of high polymers can have a significant effect on the extensional viscosity of the starch composition.
  • the high polymers useful for enhancing the melt extensibility of the starch composition used in the present invention are typically high molecular weight, substantially linear polymers.
  • high polymers that are substantially compatible with starch are most effective in enhancing the melt extensibility of the starch composition.
  • starch compositions useful for melt extensional processes typically have their extensional viscosity increased by a factor of at least 10 when a selected high polymer is added to the composition.
  • the starch compositions of present invention show an increase in the extensional viscosity of a factor of about 10 to about 500, more specifically of about 20 to about 300, still more specifically from about 30 to about 100, when a selected high polymer is added.
  • the higher the level of the high polymer the greater the increase in extensional viscosity.
  • High polymer can be added to adjust the extensional viscosity to a value of 200 to 2000 Pa•sec at a Hencky strain of 6.
  • polyacrylamide having molecular weight (MW) from 1 million to 15 million at a level of 0.001% to 0.1% can be added to comprise the starch composition.
  • the type and level of starch that is employed can also have an impact on the extensional viscosity of the starch composition.
  • the extensional viscosity increases.
  • the molecular weight of the starch within the prescribed range increases.
  • the extensional viscosity increases.
  • Temperature of the starch composition can significantly affect the extensional viscosity of the starch composition.
  • all conventional means of controlling the temperature of the starch composition can be utilized, if suitable for a particular process employed.
  • the die temperature can have a significant impact on the extensional viscosity of the starch compositions being extruded therethrough.
  • the temperature of the starch composition can range form about 20°C to about 180°C, more specifically from about 20°C to about 90°C, and even more specifically from about 50°C to about 80°C. It is to be understood that the presence or absence of solids in the starch composition can affect the required temperature thereof.
  • the Trouton ratio (Tr) can be used to express the extensional flow behavior.
  • the uniaxial extension Trouton ratio has a constant value of 3.
  • the extensional viscosity is dependent on the deformation rate ( ⁇ •) and time (t).
  • melt processable compositions of the present invention typically have a Trouton ratio of at least about 3.
  • the Trouton ratio ranges from about 10 to about 5,000, specifically from about 20 to about 1,000, and more specifically from about 30 to about 500, when measured at a processing temperature and an extension rate of 700s -1 at a Hencky strain of 6.
  • the capillary number (Ca) of the starch composition is important for melt processability.
  • the capillary number is a number representing the ratio of the viscous fluid forces to surface tension forces.
  • the capillary number is related to shear viscosity as described above, it is influenced by the same factors that affect shear viscosity and in a similar way.
  • the term "inherent” in conjunction with capillary number or surface tension indicates properties of a starch composition not influenced by outside factors, such for example, as presence of an electric field.
  • the term “effective” indicates the properties of the starch composition that has been influenced by outside factors, such for example, as presence of an electric field.
  • the melt-processable starch compositions have an inherent capillary number as they pass through the die of at least 0.01 and an effective capillary number of at least 1.0.
  • the capillary number needs to be greater than 1 for stability, and preferably greater than 5 for robust stability of the filament being formed.
  • charge repulsion counteracts the effect of surface tension so the inherent capillary number, measured without an electrical charge present, can be less than 1.
  • an electric potential is applied to the filament being formed the effective surface tension is decreased and the effective capillary number is increased based on the following equations:
  • capillary number may be expressed in varying forms
  • the inherent capillary number can be at least 1, more specifically, from 1 to 100, still more specifically from about 3 to about 50, and yet still more specifically from about 5 to about 30.
  • the starch composition herein is processed in a flowable state, which typically occurs at a temperature at least equal to or higher than its "melting temperature.” Therefore, the processing temperature range is controlled by the "melting temperature" of the starch composition, which is measured according to the Test Method described in detail herein.
  • the melting temperature of the starch composition herein ranges from about 20°C to about 180°C, more specifically from about 30°C to about 130°C, and still more specifically from about 50°C to about 90°C.
  • the melting temperature of the starch composition is a function of the amylose content of the starch (higher amylose content requires higher melting temperature), the water content, the plasticizer content and the type of plasticizer.
  • Exemplary uniaxial extensional processes suitable for the starch compositions include melt spinning, melt blowing, and spun bonding. These processes are described in detail in U. S. Patent No. 4,064,605, issued on December 27, 1977 to Akiyama et al.; U.S. Patent No. 4,418,026, issued on November 29, 1983 to Blackie et al.; U. S Patent No. 4,855,179, issued on August 8, 1989 to Bourland et al.; U. S. Patent No. 4,909,976, issued on March 20, 1990 to Cuculo et al.; U. S. Patent No. 5,145,631, issued on September 8, 1992 to Jezic; U.S. Patent No. 5,516,815, issued on May 14, 1996 to Buehler et al.; and U.S. Patent No. 5,342,335, issued on August 30, 1994 to Rhim et al..
  • the apparatus 10 may comprise, for example, a single-screw or twin-screw extruder, positive displacement pump, or a combination thereof, as is known in the art.
  • the starch solution can have a total water content, i.e. water of hydration plus added water, in the range of from about 5% to about 80%, and more specifically in the range of from about 10% to about 60% relative to a total weight of the starch material.
  • the starch material is heated to elevated temperatures sufficient to form a pseudo-thermoplastic melt. Such temperature is typically higher than the glass transition and/or melting temperature of the formed material.
  • the pseudo-thermoplastic melts of the invention are polymeric fluids having a shear rate dependent viscosity, as known in the art. The viscosity decreases with increasing shear rate as well as with increasing temperature.
  • the starch material can be heated in a closed volume in the presence of a low concentration of water, to convert the starch material to a pseudo-thermoplastic melt.
  • the closed volume can be a closed vessel or the volume created by the sealing action of the feed material as happens in the screw of extrusion equipment. Pressures created in the closed vessel will include pressures due to the vapor pressure of water as well as pressures generated due to compression of materials in the screw-barrel of the extruder.
  • a chain scission catalyst which reduces the molecular weight by splitting the glycosidic bonds in the starch macromolecules resulting in a reduction of the average molecular weight of the starch, may be used to reduce the viscosity of the pseudo-thermoplastic melt.
  • Suitable catalysts include inorganic and organic acids. Suitable inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and boric acid as well as the partial salts of polybasic acids, e.g. NaHSO 4 or NaH 2 PO 4 etc.
  • Suitable organic acids include formic acid, acetic acid, propionic acid, butyric acid, lactic acid, glycolic acid, oxalic acid, citric acid, tartaric acid, itaconic acid, succinic acid, and other organic acids known in the art, including partial salts of the polybasic acids. Hydrochloric acid, sulfuric acid, and citric acid, including mixtures thereof can be beneficially used in the present invention.
  • the reduction of the molecular weight of the non-modified starch used can be by a factor of from 2 to 5000, and more specifically by a factor of from 4 to 4000.
  • the concentration of catalysts is in the range of 10 -6 to 10 -2 mole of catalyst per mole of anhydro-glucose unit, and more specifically between 0.1x10 -3 to 5x10 -3 mole of catalyst per mole of anhydro-glucose unit of starch.
  • the starch composition is supplied into the apparatus 10 for electro-spinning production of starch filaments used in making the flexible structure 100 of the present invention.
  • the apparatus 10 comprises a housing 11 structured and configured to receive (arrow A) the starch composition 17 that can be maintained therein and extruded (arrow D) into starch filaments 17a through a jet 14 of a die head 13.
  • An annular cavity 12 can be provided to circulate (arrows B and C) a heating fluid that heats the starch composition to a desired temperature.
  • Other means for heating well known in the art, such as, those using electro-heating, pulse combustion, water- and steam-heating, etc., can be used to heat the starch composition.
  • the electric field can be applied directly to the starch solution, for example, through a electrically-charged probe, or to the housing 11 and/or extrusion die 13. If desired, the molding member 200 can be electrically charged with the electric charge opposite to the charge of the starch filaments being extruded. Alternatively, the molding member can be grounded.
  • the electric differential can be from 5kV to 60kV, and more specifically from 20kV to 40kV.
  • the plurality of extruded starch filaments can then be deposited to the molding member 200 traveling in a machine direction MD, at a certain distance from the apparatus 10. This distance should be sufficient to allow the starch filaments to elongate and then dry, and at the same time maintain a differential charge between the starch filaments exiting the jet nozzle 14 and the molding member 200.
  • a stream of drying air can be applied to the plurality of starch filaments to cause the plurality of starch filaments to turn at an angle.
  • the molding member 200 can be disposed at an angle relative to a direction of the fiber filaments when they exit the jet nozzle 14 (arrow D in Fig. 7).
  • Attenuating air can be used in combination with an electrostatic force to provide the drawing force causing the starch filaments to be attenuated, or stretched, prior to being deposited to the molding member 200.
  • Fig. 7A schematically shows an exemplary embodiment of the die head provided with one annular orifice 15 encompassing the jet nozzle 14, and three other orifices 16 equally spaced at 120° around the jet nozzle 14, for attenuating air.
  • the attenuating air as known in the art, are contemplated in the present invention.
  • the starch filaments can have a size ranging from about 0.01 decitex to about 135 decitex, more specifically from about 0.02 decitex to about 30 decitex, and even more specifically from about 0.02 decitex to about 5 decitex.
  • Starch filaments can have various cross-sectional shapes, including, but not limited to, circular, oval, rectangular, triangular, hexagonal, cross-like, star-like, irregular, and any combinations thereof.
  • One skilled in the art will understand that such a variety of shapes can be formed by differential shapes of die nozzles used to produce the starch filaments.
  • Fig. 10A schematically shows, without limitation, some possible cross-sectional areas of the starch filaments.
  • the starch filament's cross-sectional area is an area perpendicular to the starch filament's major axis and outlined by a perimeter formed by the starch filament's outside surface in a plane of the cross-section. It is believed that the greater the surface area of the starch filament (per a unit of length or weight thereof) the greater the opacity of the flexible structure 10 comprising the starch filaments. Therefore, it is believed that maximizing the surface area of the starch filaments by increasing the starch filaments' equivalent diameter can be beneficial to increase the opacity of the resulting flexible structure 100 of the present invention.
  • One way of increasing the starch filaments' equivalent diameter comprises forming starch filaments having non-circular, multi-surface, cross-sectional shapes.
  • starch filaments need not have a uniform thickness and/or cross-sectional area throughout the filament's length or a portion thereof.
  • Fig. 10 schematically shows a fragment of the starch filament having a differential cross-sectional area along its length.
  • Such differential cross-sectional areas can be formed by, for example, varying pressure within a die, or by changing at least one of the characteristics (such as, velocity, direction, etc.) of attenuating air or drying air in a melt-blowing process, or a combination meltblowing and electro-spinning process.
  • Some starch filaments may have "notches" distributed at certain intervals along the filament's length or a portion thereof. Such variations in the starch filaments' cross-sectional area along the filaments' length are believed to encourage flexibility of the filaments, facilitate the filaments' ability to mutually entangle in the flexible structure 100 being made, and positively influence the softness and flexibility of the resulting flexible structure 100 being made.
  • the notches, or other beneficial irregularities in the starch filaments can be formed by contacting the starch filaments with a surface having sharp edges or protrusions, as described below.
  • the next step of the process comprises providing a molding member 200.
  • the molding member 200 can comprise a patterned cylinder (not shown) or other pattern-forming member, such as a belt or a band.
  • the molding member 200 comprises a filament-contacting side 201 and a backside side 202 opposite to the filament-contacting side 201.
  • a fluid pressure differential for example, a vacuum pressure, that can be present beneath the belt or within the drum
  • the starch filaments are deposited onto the filament-contacting side 201.
  • the second side 202 typically contacts the equipment, such as support rolls, guiding rolls, a vacuum apparatus, etc., as required by a specific process.
  • the filament-contacting side 201 comprises a three-dimensional pattern of protrusions and/or depressions. Typically (although not necessarily), that pattern is non-random and repeating.
  • the three-dimensional pattern of the filament contacting side 201 can comprise a substantially continuous pattern (Fig. 4), a substantially semi-continuous pattern (Fig. 5), a pattern comprising a plurality of discrete protuberances (Fig. 5), or any combination thereof.
  • the molding member 200 can comprise a belt or band that is macroscopically monoplanar when it lies in a reference X-Y plane, wherein a Z-direction is perpendicular to the X-Y plane.
  • the flexible flexible structure 100 can be thought of as macroscopically monoplanar and lying in a plane parallel to the X-Y plane. Perpendicular to the X-Y plane is the Z-direction along which extends a caliper, or thickness, of the flexible structure 100, or elevations of the differential regions of the molding member 200 or of the flexible structure 100.
  • the molding member 200 comprising a belt may be executed as a press felt.
  • a suitable press felt for use according to the present invention may be made according to the teachings of U.S. Patent Nos. 5,549,790, issued Aug. 27, 1996 to Phan; 5,556,509, issued Sept. 17, 1996 to Trokhan et al.; 5,580,423, issued Dec. 3, 1996 to Ampulski et al.; 5,609,725, issued Mar. 11, 1997 to Phan; 5,629,052 issued May 13, 1997 to Trokhan et al.; 5,637,194, issued June 10, 1997 to Ampulski et al.; 5,674,663, issued Oct. 7, 1997 to McFarland et al.; 5,693,187 issued Dec.
  • the molding member 200 may be executed as a press felt according to the teachings of U.S. Pat. No. 5,569,358 issued Oct. 29, 1996 to Cameron.
  • the molding member 200 comprises a resinous framework 210 joined to a reinforcing element 250.
  • the resinous framework 210 can have a certain pre-selected pattern.
  • Fig. 4 shows the substantially continuous framework 210 having a plurality of apertures 220 therethrough.
  • the reinforcing element 250 can be substantially fluid-permeable.
  • the fluid-permeable reinforcing element 250 may comprise a woven screen, or an apertured element, a felt, or any combination thereof.
  • the portions of the reinforcing element 250 registered with apertures 220 in the molding member 200 prevent starch filaments from passing through the molding member 200, and thereby reduce the occurrences of pinholes in the resulting flexible structure 100.
  • a nonwoven element, screen, net, press felt or a plate or film having a plurality of holes therethrough may provide adequate support and strength for the framework 210.
  • Suitable reinforcing element 250 may be made according to U.S. Pat. Nos. 5,496,624, issued March 5, 1996 to Stelljes, et al., 5,500,277 issued March 19, 1996 to Trokhan et al., and 5,566,724 issued October 22, 1996 to Trokhan et al..
  • the reinforcing element 250 may comprise a felt, also referred to as a "press felt” as is used in conventional papermaking.
  • the framework 210 may be applied to the reinforcing element 250, as taught by U.S. Patents 5,549,790, issued Aug. 27, 1996 to Phan; 5,556,509, issued Sept. 17, 1996 to Trokhan et al.; 5,580,423, issued Dec. 3, 1996 to Ampulski et al.; 5,609,725, issued Mar.
  • the reinforcing element 250 may be fluid-impermeable.
  • the fluid-impermeable reinforcing element 250 can comprise, for example, a polymeric resinous material, identical to, or different from, the material used for making a framework 210 of the molding member 200 of the present invention; a plastic material; a metal; any other suitable natural or synthetic material; or any combination thereof.
  • the fluid-impermeable reinforcing element 250 will cause the molding member 10, as a whole, to be also fluid-impermeable. It is to be understood that the reinforcing element 250 may be partially fluid-permeable and partially fluid-impermeable.
  • the molding member 200 can be fluid-permeable, fluid-impermeable, or partially fluid-permeable. In a partially fluid-permeable molding member 200, only a portion or portions of a macroscopical area or areas of the molding member 200 is fluid-permeable.
  • the reinforcing element 250 comprising a Jacquard weave
  • Illustrative belts having the Jacquard weave can be found in U.S. Pat. Nos. 5,429,686 issued 7/4/95 to Chiu, et al.; 5,672,248 issued 9/30/97 to Wendt, et al.; 5,746,887 issued 5/5/98 to Wendt, et al.; and 6,017,417 issued 1/25/00 to Wendt, et al., the disclosures of which are incorporated herein by reference for the limited purpose of showing a principal construction of the Jacquard weave.
  • the present invention contemplates the molding member 200 comprising the filament-contacting side 201 having a Jacquard-weave pattern.
  • a Jacquard-weave pattern may be utilized as a forming member 500, a molding member 200, a pressing surface, etc.
  • a jacquard weave is reported in the literature to be particularly useful where one does not wish to compress or imprint a structure in a nip, such as typically occurs upon transfer to a Yankee drying drum.
  • one, several, or all of the apertures 220 of the molding member 200 may be "blind,” or “closed,” as described in US Patent 5,972,813, issued to Polat et al. on Oct. 26, 1999.
  • polyurethane foams, rubber, and silicone can be used to render the apertures 220 fluid-impermeable.
  • An embodiment of the molding member 200 shown in Fig. 6 comprises a plurality of suspended portions 219 extending (typically laterally) from a plurality of base portions 211.
  • the suspended portions 219 are elevated from the reinforcing element 250 to form void spaces 215 into which the starch filaments of the present invention can be deflected to form cantilever portions 129, as described above with reference to Fig. 3.
  • the molding member 200 comprising suspended portions 219 may comprise a multi-layer structure formed by at least two layers (211, 212) joined together in a face-to-face relationship (Fig. 6).
  • Each of the layers can comprise a structure similar to one of the several patents described above.
  • Each of the layers (211, 212) can have at least one aperture (220, Figs.
  • the joined layers are positioned such that the at least one aperture of one layer is superimposed (in the direction perpendicular to the general plane of the molding member 200) with a portion of the framework of the other layer, which portion forms the suspended portion 219 described herein above.
  • Another embodiment of the molding member comprising a plurality of suspended portions can be made by a process of differential curing of a layer of a photosensitive resin, or other curable material, through a mask comprising transparent regions and opaque regions.
  • the opaque regions comprise regions having differential opacity, for example, regions having a relatively high opacity (non-transparent, such as black) and regions having a relatively low, partial, opacity (i. e. having some transparency).
  • the non-transparent regions of the mask shield first areas of the coating from the curing radiation to preclude curing of the first areas of the coating through the entire thickness of the coating.
  • the partial-opacity regions of the mask only partially shield second areas of the coating to allow the curing radiation to cure the second areas to a predetermined thickness less than the thickness of the coating (beginning from the filament-receiving side of the coating towards the second side thereof).
  • the transparent regions of the mask leave third areas of the coating unshielded to allow the curing radiation to cure the third areas through the entire thickness of the coating.
  • the resulting hardened framework has a filament-contacting side 201 formed from the filament-receiving side of the coating and a backside 202 formed from the second side of the coating.
  • the resulting framework has a plurality of bases 211 comprising the backside 202 and formed from the third areas of the coating and a plurality of suspended portions 219 comprising the web-contacting side 201 and formed from the second areas of the coating.
  • the plurality of bases may comprise a substantially continuous pattern, a substantially semi-continuous pattern, a discontinuous pattern, or any combination thereof, as discussed above.
  • the suspended portions 219 extend, at an angle (typically, but not necessarily, at about 90°) from the plurality of bases and are spaced from the backside 202 of the resulting framework to form void spaces between the suspended portions and the backside 201.
  • the void spaces 215 are formed between the suspended portions 219 and the reinforcing element 250, as best shown in Fig. 6.
  • the next step comprises depositing the plurality of pseudo-thermoplastic starch filaments on the filament contacting side 201 of the molding member 200, as schematically shown in Figs. 7-9, and causing the plurality of starch filaments to at least partially conform to the three-dimensional pattern of the molding member 200.
  • the starch filaments 17b are deposited on the three-dimensional filament contacting side 201 of a molding member 200.
  • the molding member 200 comprises an endless belt continuously traveling in a machine direction MD, as schematically shown in Figs. 7-9.
  • the starch filaments can then be joined to one another and mutually entangled through a variety of conventional techniques.
  • the plurality of starch filaments may first be deposited not to the molding member 10, but to a forming member 500, as schematically shown in Fig. 9. This step is optional and can be utilized to facilitate uniformity in the basis weight of the plurality of starch filaments throughout a width of the structure 10 being made.
  • the forming member 500 comprising a wire is contemplated by the present invention. In an exemplary embodiment of Fig. 9, the forming member 500 travels in the machine direction about rolls 500a and 500b.
  • the forming member is fluid permeable, and a vacuum apparatus 550 located under the forming member 500 and applying fluid pressure differential to the plurality of starch filaments disposed thereon encourages a more-or-less even distribution of the starch filaments throughout the receiving surface of the forming member 500.
  • the forming member 200 can also be used to form various irregularities in the starch filaments, particularly on the surface of the filaments.
  • a filament-receiving surface of the forming member can comprise a variety of sharp edges (not shown) structured to imprint still relatively soft starch filaments deposited thereto, to create notches (schematically shown in Fig. 11) or other irregularities in the starch filaments, that can be beneficial to the flexible structure 100 being made, as described above.
  • the plurality of filaments can be transferred from the forming member 500 to the molding member 200 by any conventional means known in the art, for example, by a vacuum shoe 600 that applies a vacuum pressure which is sufficient to cause the plurality of starch filaments disposed on the forming member 500 to separate therefrom and adhere to the molding member 200.
  • the molding member 200 may have a linear velocity that is less that that of the forming member 500.
  • the use of such a velocity differential at the transfer point is commonly known in the papermaking arts and can be used for so called "microcontraction" that is typically believed to be efficient when applied to low-consistency, wet webs.
  • wet-microcontraction involves transferring the web having a low fiber-consistency from a first member (such as a foraminous member) to a second member (such as a loop of open-weave fabric) moving slower than the first member.
  • a first member such as a foraminous member
  • a second member such as a loop of open-weave fabric
  • the starch filaments can be formed and the plurality of starch filaments can be maintained in a sufficiently flexible condition by the time of transferal from a relatively slower moving support (such, for example, as the forming member 500) to a relatively faster moving support (such as, for example, the molding member 200), it may be possible to effectively subject the plurality of starch filaments to microcontraction, thereby foreshortening the flexible structure 100 being made.
  • the velocity of the molding member 200 can be from about 1% to about 25% greater than that of the forming member 500.
  • Fig. 9A shows an embodiment of the process according to the present invention, wherein the starch filaments can be deposited to the molding member 200 at an angle A that can be from 1° to 89°, and more specifically, from about 5° to about 85°. This embodiment is believed to be especially beneficial when the molding member 200 having suspended portions 219 is used.
  • Such an "angled" deposition of the starch filaments 17a to the molding member 200 makes the void spaces 215 formed between the suspended portions 219 and the reinforcing element 250 more accessible to long and flexible starch filaments 17a, and encourages the starch filaments to more easily fill the void spaces 215.
  • Fig. 9A shows an embodiment of the process according to the present invention, wherein the starch filaments can be deposited to the molding member 200 at an angle A that can be from 1° to 89°, and more specifically, from about 5° to about 85°.
  • This embodiment is believed to be especially beneficial when the molding member 200 having suspended portions 219 is used.
  • the starch filaments 17a are deposited to the molding member 200 in two steps, so that both kinds of the void spaces 219 -- upstream void spaces 215a and downstream void spaces 215b -- can benefit from the angled deposition of the filaments to the molding member 200.
  • a downstream angle A may be equal or different from an upstream angle B.
  • the plurality of starch filaments As soon as the plurality of starch filaments is disposed on the filament contacting side 201 of the molding member 200, the plurality of filaments at least partially conforms to its three-dimensional pattern.
  • various means can be utilized to cause or encourage the starch filaments to conform to the three-dimensional pattern of the molding member 200.
  • One method comprises applying a fluid pressure differential to the plurality of starch filaments. This method can be especially beneficial when the molding member 200 is fluid-permeable.
  • a vacuum apparatus 550 disposed at the backside 202 of the fluid-permeable molding member 200 can be arranged to apply a vacuum pressure to the molding member 200 and thus to the plurality of starch filaments disposed thereon, Fig. 8. Under the influence of the vacuum pressure, some of the starch filaments can be deflected into the apertures 220 and/or the void spaces 215 of the molding member 200 and otherwise conform to the three-dimensional pattern thereof.
  • all three regions of the flexible structure 100 may have generally equivalent basis weights.
  • deflecting a portion of starch filaments into the apertures 220 one can decrease the density of the resulting pillows 120 relative to the density of the first, imprinted, regions 110.
  • the regions 110 that are not deflected in the apertures 220 may be imprinted by compressing flexible structure in a compression nip. If imprinted, the density of the imprinted regions 110 is increased relative to the density of the pillows 120 and the density of the third region 130.
  • the densities of the regions 110 not deflected into the apertures 220 and the density of the third region 130 are higher than the density of the pillows 120.
  • the third region 130 will likely have a density intermediate those of the imprinted regions 110 and the pillows 120.
  • the flexible structure 100 may be thought of as having three different densities.
  • the highest density region will be the high density imprinted region 110.
  • the imprinted region 110 corresponds in position and geometry to the framework 210 of the molding member 200.
  • the lowest density region of the flexible structure 100 will be that of the pillows 120, corresponding in position and geometry to the apertures 220 of the molding member 200.
  • the third region 130, corresponding to the synclines 230 in the molding member 200, will have a density intermediate those of the pillows 120 and the imprinted region 110.
  • the "synclines" 230 are surfaces of the framework 210 having a Z-direction vector component extending from the filament-receiving side 201 of the molding member 200 towards the backside 202 thereof.
  • the synclines 230 do not extend completely through the framework 210, as do the apertures 220. Thus, the difference between a syncline 230 and the apertures 220 may be thought of as the aperture 220 represents a through hole in the framework 210, whereas a syncline 230 represents a blind hole, fissure, chasm, or notch in the framework 210.
  • the three regions of the structure 100 may be thought of as being disposed at three different elevations.
  • the elevation of a region refers to its distance from a reference plane (i. e., X-Y plane).
  • the reference plane can be visualized as horizontal, wherein the elevational distance from the reference plane is vertical.
  • the elevation of a particular region of the starch filament structure 100 may be measured using any non-contacting measurement device suitable for such purpose as is well known in the art.
  • a particularly suitable measuring device is a non-contacting Laser Displacement Sensor having a beam size of 0.3 X 1.2 millimeters at a range of 50 millimeters.
  • Suitable non-contacting Laser Displacement Sensors are sold by the Idec Company as models MX1A/B.
  • a contacting stylis gauge as is known in the art, may be utilized to measure the different elevations.
  • Such a stylis gauge is described in U.S. Patent 4,300,981 issued to Carstens, the disclosure of which is incorporated herein by reference.
  • the structure 100 according to the present invention is placed on the reference plane with the imprinted region 110 in contact with the reference plane.
  • the pillows 120 and the third region 130 extend vertically away from the reference plane. Differential elevations of the regions 110, 120, and 130 can also be formed by using the molding member 200 having differential depths or elevations of its three-dimensional pattern, as schematically shown in Fig. 5A.
  • Such three-dimensional patterns having differential depths/elevations can be made by sanding pre-selected portions of the molding member 200 to reduce their elevation.
  • the molding member 200 comprising a curable material can be made by using a three-dimensional mask.
  • a three-dimensional mask comprising differential depths/elevations of its depressions/protrusions, one can form a corresponding framework 210 also having differential elevations.
  • Other conventional techniques of forming surfaces with differential elevation can be used for the foregoing purposes.
  • the backside of the molding member can be "textured" to form microscopical surface irregularities.
  • Those surface irregularities can be beneficial in some embodiments of the molding member 200, because they prevent formation of a vacuum seal between the backside 202 of the molding member 200 and a surface of the papermaking equipment (such as, for example, a surface of the vacuum apparatus), thereby creating a "leakage" therebetween and thus mitigating undesirable consequences of an application of a vacuum pressure in a through-air-drying process of making the flexible structure 100 of the present invention.
  • a surface irregularities can be beneficial in some embodiments of the molding member 200, because they prevent formation of a vacuum seal between the backside 202 of the molding member 200 and a surface of the papermaking equipment (such as, for example, a surface of the vacuum apparatus), thereby creating a "leakage" therebetween and thus mitigating undesirable consequences of an application of a vacuum pressure in a through-air-drying process of making the flexible structure 100 of the present invention.
  • Other methods of creating such a leakage are disclosed in U.S. Patents 5,718,806; 5,741,402;
  • the leakage can also be created using so-called "differential light transmission techniques" as described in U.S. patents 5,624,790; 5,554,467; 5,529,664; 5,514,523; and 5,334,289.
  • the molding member can be made by applying a coating of photosensitive resin to a reinforcing element that has opaque portions, and then exposing the coating to light of an activating wavelength through a mask having transparent and opaque regions, and also through the reinforcing element.
  • Another way of creating backside surface irregularities comprises the use of a textured forming surface, or a textured barrier film, as described in U.S. patents 5,364,504; 5,260,171; and 5,098,522.
  • the molding member can be made by casting a photosensitive resin over and through the reinforcing element while the reinforcing element travels over a textured surface, and then exposing the coating to light of an activating wavelength through a mask which has transparent and opaque regions.
  • Such means as a vacuum apparatus 550 applying a vacuum (i. e., negative, less than atmospheric) pressure to the plurality of filaments through the fluid-permeable molding member 200, or a fan (not shown) applying a positive pressure to the plurality of filaments can be used to facilitate deflection of the plurality of filaments into the three-dimensional pattern of the molding member.
  • a vacuum apparatus 550 applying a vacuum (i. e., negative, less than atmospheric) pressure to the plurality of filaments through the fluid-permeable molding member 200, or a fan (not shown) applying a positive pressure to the plurality of filaments can be used to facilitate deflection of the plurality of filaments into the three-dimensional pattern of the molding member.
  • Fig. 9 schematically shows an optional step of the process of the present invention, wherein the plurality of starch filaments is overlaid with a flexible sheet of material 800 comprising an endless band traveling around rolls 800a and 800b and contacting the plurality of filaments. That is, the plurality of filaments is sandwiched, for a certain period of time, between the molding member 200 and the flexible sheet of material 800.
  • the flexible sheet of material 800 can have air-permeability less than that of the molding member 200, and in some embodiments can be air-impermeable.
  • An application of a fluid pressure differential P to the flexible sheet 800 causes deflection of at least a portion of the flexible sheet towards, and in some instances into, the three-dimensional pattern of the molding member 200, thereby forcing the plurality of starch filaments to closely conform to the three-dimensional pattern of the molding member 200.
  • US patent 5,893,965 the disclosure of which is incorporated herein by reference, describes a principle arrangement of an equipment and a process utilizing the flexible sheet of material.
  • mechanical pressure can also be used to facilitate formation of the three-dimensional microscopical pattern of the flexible structure 100 of the present invention.
  • a mechanical pressure can be created by any suitable press surface, comprising, for example a surface of a roll or a surface of a band.
  • Fig. 8 shows two exemplary embodiments of pressing surface.
  • a pair or several pairs of press roll 900a and 900b, and 900c and 900d can be used to force the starch filaments disposed on the molding member 200 to more fully conform to the three-dimensional pattern thereof.
  • the pressure exerted by the press rolls can be phased, if desired, for example, the pressure created between the rolls 900c and 900d can be greater than that between the rolls 900 a and 900b.
  • an endless press band 950 traveling about rolls 950a and 950b can be pressed against a portion of the filament side 201 of the molding member 200, to impress the flexible structure 100 therebetween.
  • the press surface can be smooth or have a three-dimensional pattern of its own.
  • the press surface can be used as an embossing device, to form a distinctive micro-pattern of protrusions and/or depressions in the flexible structure 100, in cooperation with or independently from the three-dimensional pattern of the molding member 200.
  • the press surface can be used to deposit a variety of additives, such for example, as softeners, and ink, to the flexible structure 200 being made.
  • Conventional techniques, such as, for example, ink roll 910, or spraying device (or shower) 920 may be used to directly or indirectly deposit a variety of additives to the flexible structure 1200 being made.
  • the structure 100 may optionally be foreshortened, as is known in the art.
  • Foreshortening can be accomplished by creping the structure 100 from a rigid surface, and more specifically from a cylinder, such as, for example, a cylinder 290 schematically shown in Fig. 9. Creping is accomplished with a doctor blade 292, as is well known in the art. Creping may be accomplished according to U.S. Patent 4,919,756, issued April 24, 1992 to Sawdai. Alternatively or additionally, foreshortening may be accomplished via microcontraction, as described above.
  • the flexible structure 100 that is foreshortened is typically more extensible in the machine direction than in the cross machine direction and is readily bendable about hinge lines formed by the foreshortening process, which hinge lines extend generally in the cross-machine direction, i. e., along the width of the flexible structure 100.
  • the flexible structure 100 which is not creped and/or otherwise foreshortened, is contemplated to be within the scope of the present invention.
  • a variety of products can be made using the flexible structure 100 of the present invention.
  • the resultant products may find use in filters for air, oil and water; vacuum cleaner filters; furnace filters; face masks; coffee filters, tea or coffee bags; thermal insulation materials and sound insulation materials; nonwovens for one-time use sanitary products such as diapers, feminine pads, and incontinence articles; biodegradable textile fabrics for improved moisture absorption and softness of wear such as microfiber or breathable fabrics; an electrostatically charged, structured web for collecting and removing dust; reinforcements and webs for hard grades of paper, such as wrapping paper, writing paper, newsprint, corrugated paper board, and webs for tissue grades of paper such as toilet paper, paper towel, napkins and facial tissue; medical uses such as surgical drapes, wound dressing, bandages, dermal patches and self-dissolving sutures; and dental uses such as dental floss and toothbrush bristles.
  • the flexible structure may also include odor absorbants, termite repellents, insecticides, rodenticides, and the like, for specific uses.
  • the resultant product absorbs water and oil and may find use in oil or water spill clean-up, or controlled water retention and release for agricultural or horticultural applications.
  • the resultant starch filaments or fiber webs may also be incorporated into other materials such as saw dust, wood pulp, plastics, and concrete, to form composite materials, which can be used as building materials such as walls, support beams, pressed boards, dry walls and backings, and ceiling tiles; other medical uses such as casts, splints, and tongue depressors; and in fireplace logs for decorative and/or burning purpose.
  • the extensional viscosity is measured using a capillary rheometer (Model Rheograph 2003, manufactured by Goettfert). The measurements are conducted using a semi-hyperbolic die design with an initial diameter(D initial ) of 15mm, a final diameter(D final ) of 0.75mm and a length(L) of 7.5mm.
  • the die is attached to the lower end of a barrel, which is held at a fixed test temperature (t) which corresponds to the temperature at which the starch composition is to be processed.
  • the test temperature (processing temperature) is a temperature above the melting point of a sample starch composition.
  • the sample starch composition is preheated to the die temperature is loaded into the barrel section of the rheometer, and substantially fills the barrel section. If after the loading, air bubbles to the surface, compaction prior to running the test is used to rid the molten sample of entrapped air.
  • a piston is programmed to push the sample from the barrel through the hyperbolic die at a chosen rate. As the sample goes from the barrel through the orifice die, the sample experiences a pressure drop.
  • Extensional Viscosity (delta P/extension rate/E h ) • 10 +5 ), where Extensional Viscosity is in Pascal-Seconds, delta P is the pressure drop in bars, extension rate is the flow rate of the sample through the die in sec -1 , and E h is dimensionless Hencky strain. Hencky strain is the time or history dependent strain. The strain experienced by a fluid element in a non-Newtonian fluid is dependent on its kinematic history, that is
  • the weight-average molecular weight (Mw) and molecular weight distribution (MWD) of starch are determined by Gel Permeation Chromatography (GPC) using a mixed bed column. Parts of the instrument are as follows: Pump Waters Model 600E System controller Waters Model 600E Autosampler Waters Model 717 Plus Column PL gel 20 ⁇ m Mixed A column (gel molecular weight ranges from 1,000 to 40,000,000) having a length of 600 mm and an internal diameter of 7.5 mm. Detector Waters Model 410 Differential Refractometer GPC software Waters Millennium® software
  • the column is calibrated with Dextran standards having molecular weights of 245,000; 350,000; 480,000; 805,000; and 2,285,000.
  • Dextran calibration standards are available from American Polymer Standards Corp., Mentor, OH.
  • the calibration standards are prepared by dissolving the standards in the mobile phase to make a solution of about 2 mg/ml. The solution sits undisturbed overnight. Then it is gently swirled and filtered through a syringe filter (5 ⁇ m Nylon membrane, Spartan-25, available from VWR) using a syringe (5 ml, Norm-Ject, available from VWR).
  • the starch sample is prepared by first making a mixture of 40wt% starch in tap water, with heat applied until the mixture gelatinizes. Then 1.55 grams of the gelatinized mixture is added to 22 grams of mobile phase to make a 3 mg/ml solution which is prepared by stirring for 5 minutes, placing the mixture in an oven at 105°C for one hour, removing the mixture from the oven, and cooling to room temperature. The solution is filtered using the syringe and syringe filter as described above.
  • the filtered standard or sample solution is taken up by the autosampler to flush out previous test materials in a 100 ⁇ l injection loop and inject the present test material into the column.
  • the column is held at 70°C.
  • the sample eluded from the column is measured against the mobile phase background by a differential refractive index detector held at 50°C and with the sensitivity range set at 64.
  • the mobile phase is DMSO with 0.1% w/v LiBr dissolved therein.
  • the flow rate is set at 1.0ml/min and in the isocratic mode (i.e., the mobile phase is constant during the run).
  • Each standard or sample is run through the GPC three times and the results are averaged.
  • MWD weight average molecular weight/number average molecular weight
  • Thermal properties of the present starch compositions are determined using a TA Instruments DSC-2910 which has been calibrated with an indium metal standard, which has an melting temperature (onset) of 156.6°C and a heat of melting of 6.80 calories per gram, as reported in the chemical literature. Standard DSC operating procedure per manufacturer's Operating Manual is used. Due to the volatile evolution (e.g., water vapor) from the starch composition during a DSC measurement, a high volume pan equipped with an o-ring seal is used to prevent the escape of volatiles from the sample pan. The sample and an inert reference (typically an empty pan) are heated at the same rate in a controlled environment.
  • an inert reference typically an empty pan
  • the DSC instrument measures the heat flow to or from the sample versus that of the inert reference.
  • the instrument is interfaced with a computer for controlling the test parameters (e.g., the heating/cooling rate), and for collecting, calculating and reporting the data.
  • the sample is weighed into a pan and enclosed with an o-ring and a cap.
  • a typical sample size is 25-65 milligrams.
  • the enclosed pan is placed in the instrument and the computer is programmed for the thermal measurement as follows:
  • the computer calculates and reports the thermal analysis result as differential heat flow ( ⁇ H) versus temperature or time.
  • ⁇ H differential heat flow
  • the differential heat flow is normalized and reported on per weight basis (i.e, cal/mg).
  • a differential of the ⁇ H v. time/temperature plot may be employed to more easily determine a glass transition temperature.
  • a sample composition is made by mixing the components with heat and stirring until a substantially homogeneous mixture is formed.
  • the melt composition is cast into a thin film by spreading it over a Teflon® sheet and cooling at ambient temperature.
  • the film is then dried completely (i.e., no water in the film/composition) in an oven at 100°C.
  • the dried film is then equilibrated to room temperature.
  • the equilibrated film is ground into small pellets.
  • % Solids (dried weight of ground sample & pan - weight of pan) (first weight of ground sample & pan - weight of pan) • 100
  • the film sample Prior to testing, the film sample is conditioned at a relative humidity of 48% - 50% and at a temperature of 22°C to 24°C until a moisture content of about 5% to about 16% is achieved.
  • the moisture content is determined by TGA (Thermo Gravimetric Analysis).
  • TGA Thermo Gravimetric Analysis
  • Preconditioned samples are cut to a size greater than the size of the foot used to measure the caliper.
  • the foot to be used is a circle with an area of 3.14 square inches.
  • the sample is placed on a horizontal flat surface and confined between the flat surface and a load foot having a horizontal loading surface, where the load foot loading surface has a circular surface area of about 3.14 square inches and applies a confining pressure of about 15 g/square cm (0.21 psi) to the sample.
  • the caliper is the resulting gap between the flat surface and the load foot loading surface.
  • Such measurements can be obtained on a VIR Electronic Thickness Tester Model II available from Thwing-Albert, Philadelphia, Pa. The caliper measurement is repeated and recorded at least five times. The result is reported in mils.

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Claims (21)

  1. Verfahren zum Herstellen von Endlos-Stärkefilamente, welches Verfahren die Schritte umfasst:
    (a) Bereitstellen einer Stärkezusammensetzung, aufweisend 10% bis 80 Gew.% modifizierte, aufgeschlossene Stärke und 20% bis 90 Gew.% eines Additivs, worin die Stärke eine massegemittelte relative Molekülmasse von 1.000 bis 2.000.000 hat und worin die Stärkezusammensetzung eine Dehnviskosität von 50 Pa·s bis 20.000 Pa·s hat und eine logarithmische Kapillaritätszahl von mindestens 0,05; und
    (b) Elektrospinnen der Stärkezusammensetzung, wodurch die Stärkefilamente mit einer Größe von 0,001 dtex bis 135 dtex erzeugt werden.
  2. Verfahren nach Anspruch 1, bei welchem die Stärkezusammensetzung eine logarithmische Kapillarzahl von mindestens 1 hat.
  3. Verfahren nach einem der vorgenannten Ansprüche, bei welchem der Schritte der Bereitstellung einer Stärkezusammensetzung die Bereitstellung einer Stärkezusammensetzung umfasst, worin 20% bis 99 Gew.% Amylopektin sind.
  4. Verfahren nach einem der vorgenannten Ansprüche, bei welchem die Stärkezusammensetzung eine Dehnviskosität von 100 Pa·s bis 15.000 Pa·s hat.
  5. Verfahren nach einem der vorgenannten Ansprüche, bei welchem die Stärkezusammensetzung 20% bis 70 Gew.% Stärke aufweist und 30% bis 80 Gew.% Additive und worin die Stärkezusammensetzung eine Dehnviskosität von 200 Pa·s bis 10.000 Pa·s hat.
  6. Verfahren nach einem der vorgenannten Ansprüche, bei welchem die Stärkezusammensetzung eine Genviskosität von 200 Pa·s bis 10.000 Pa·s und eine logarithmische Kapillarzahl von 3 bis 50 hat.
  7. Verfahren nach einem der vorgenannten Ansprüche, bei welchem die Stärkezusammensetzung eine Dehnviskosität von 300 Pa·s bis 5.000 Pa·s und eine Kapillarzahl von 5 bis 30 hat.
  8. Verfahren nach einem der vorgenannten Ansprüche, bei welchem der Schritt der Bereitstellung einer Stärkezusammensetzung das Bereitstellen einer Stärkezusammensetzung umfasst, die ferner 0,0005% bis 5 Gew.% eines Hochpolymers mit einer mittleren relativen Molekülmasse von mindestens 500.000 aufweist, wobei das Hochpolymer mit der Stärke weitgehend kompatibel ist.
  9. Verfahren nach einem der vorgenannten Ansprüche, bei welchem das Additiv ausgewählt ist aus der Gruppe, bestehend aus Weichmachern und Streckmitteln.
  10. Verfahren nach einem der vorgenannten Ansprüche, bei welchem die Stärkezusammensetzung ferner 5% bis 95 Gew.% eines Proteins aufweist, wobei das Protein ein von Mais deriviertes Protein aufweist, ein von Sojabohnen deriviertes Protein, ein von Weizen deriviertes Protein oder eine beliebige Kombination davon.
  11. Verfahren nach einem der vorgenannten Ansprüche, ferner umfassend einen Schritt des Verfeinerns der Stärkefilamente mit Luftströmen.
  12. Verfahren zum Herstellen einer flexible, Stärkefilamente aufweisenden Struktur, welches Verfahren die Schritte umfasst:
    (a) Bereitstellen einer Stärkezusammensetzung, aufweisend 10% bis 80 Gew.% modifizierte, aufgeschlossene Stärke und 20% bis 90 Gew.% eines Additivs, worin die Stärke eine massegemittelte relative Molekülmasse von 1.000 bis 2.000.000 hat und wobei die Stärkezusammensetzung eine Dehnviskosität von 100 Pa·s bis 10.000 Pa·s hat und eine logarithmische Kapillarzahl von mindestens 0,05;
    (b) Bereitstellen eines Teils zum Formen, das über eine dreidimensionale Filament aufnehmende Seite und eine dazu gegenüberliegende Rückseite verfügt, wobei die Filament aufnehmende Seite ein im Wesentlichen kontinuierliches Muster aufweist, ein im Wesentlichen halbkontinuierliches Muster, ein diskretes Muster oder eine beliebige Kombination davon;
    (c) Elektrospinnen der Stärkezusammensetzung, wodurch eine Vielzahl von Stärkefilamenten erzeugt wird; und
    (d) Ablegen der Vielzahl von Stärkefilamenten auf der Filament aufnehmenden Seite des Teils zum Formen, worin die Stärkefilamente die Form des dreidimensionalen Musters der Filament aufnehmenden Seite annehmen.
  13. Verfahren nach Anspruch 12, bei welchem die Stärkezusammensetzung ferner ein Hochpolymer mit einer massegemittelten relativen Molekülmasse von mindestens 500.000 aufweist.
  14. Verfahren nach einem der Ansprüche 12 und 13, bei welchem der Schritt des Elektrospinnens der Stärkezusammensetzung das Elektrospinnen der Stärkezusammensetzung durch eine Düse umfasst.
  15. Verfahren nach einem der Ansprüche 12 bis 14, ferner umfassend einen Schritt des Verfeinerns der Stärkefilamente mit Luft.
  16. Verfahren nach einem der Ansprüche 12 bis 15, bei welchem der Schritt der Bereitstellung eines Teils zum Formen das Bereitstellen eines Teils zum Formen umfasst, das zu einem kontinuierlichen Durchlauf in Faserlaufrichtung strukturiert ist.
  17. Verfahren nach einem der Ansprüche 12 bis 16, bei welchem der Schritt der Bereitstellung eines Teils zum Formen das Bereitstellen eines Teils zum Formen umfasst, das mit Hilfe eines verstärkenden Elementes geformt ist, das auf einer ersten Erhöhung angeordnet ist, und ein Harzgerippe, das mit dem verstreckenden Element in einer unmittelbar gegenüberliegenden Beziehung verbunden ist und von dem verstärkenden Element unter Bildung einer zweiten Erhöhung nach außen ragt.
  18. Verfahren nach Anspruch 17, bei welchem das Teil zum Formen für Fluid durchlässig ist und eine Vielzahl von verflochtenen Garnen, einen Filz oder eine beliebige Kombination davon aufweist.
  19. Verfahren nach Anspruch 17, bei welchem das Harzgerippe eine Vielzahl von Basisträgern aufweist, die sich von dem verstärkenden Element nach außen erstrecken, und eine Vielzahl von Auslegerabschnitten, die sich seitlich von den Basisträgern in der zweiten Erhöhung unter Erzeugung von Hohlräumen zwischen den Auslegeabschnitten und dem verstärkenden Element erstrecken, worin die Vielzahl von Basisträgern und die Vielzahl von Auslegerabschnitten in Kombination die dreidimensionale Filament aufnehmende Seite des Teils zum Formen bilden.
  20. Verfahren nach einem der Ansprüche 12 bis 19, bei welchem der Schritt des Ablegens der Vielzahl von Stärkefilamenten auf die Filament aufnehmende Seite des Teils zum Formen das Anlegen einer Fluiddruckdifferenz an der Vielzahl von Stärkeelementen umfasst.
  21. Verfahren nach Anspruch 1, bei welchem der Schritt des Bereitstellens einer Stärkezusammensetzung ferner ein Hochpolymer umfasst.
EP00127813A 2000-12-12 2000-12-19 Elektrospinnverfahren zur Herstellung von Stärkefilamenten für flexible Strukturen Expired - Lifetime EP1217107B1 (de)

Priority Applications (14)

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NZ508818A NZ508818A (en) 2000-12-12 2000-12-12 Electro-spinning process for making starch filaments for flexible structure
ZA200007425A ZA200007425B (en) 2000-12-12 2000-12-12 Electro-spinning process for making starch filaments for flexible structure.
AU72219/00A AU760124B2 (en) 2000-12-12 2000-12-13 Electro-spinning process for making starch filaments for flexible structure
NO20006375A NO20006375L (no) 2000-12-12 2000-12-14 Elektrospinneprosess for fremstilling av filamenter for en fleksible strukturer
SG200007497A SG93288A1 (en) 2000-12-12 2000-12-15 Electro-spinning process for making starch filaments for flexible structure
ES00127813T ES2241543T3 (es) 2000-12-12 2000-12-19 Proceso de electro-hilatura para obtener filamentos de almidon para estructuras flexibles.
CZ20004785A CZ20004785A3 (cs) 2000-12-12 2000-12-19 Způsob elektrozvlákňování pro přípravu ąkrobových filamentů pro flexibilní strukturu
EP00127813A EP1217107B1 (de) 2000-12-12 2000-12-19 Elektrospinnverfahren zur Herstellung von Stärkefilamenten für flexible Strukturen
AT00127813T ATE294882T1 (de) 2000-12-12 2000-12-19 Elektrospinnverfahren zur herstellung von stärkefilamenten für flexible strukturen
RU2000131894/04A RU2201945C2 (ru) 2000-12-12 2000-12-19 Способ электроформования крахмальных нитей для гибкой структуры
SK1963-2000A SK19632000A3 (sk) 2000-12-12 2000-12-19 Spôsob elektrozvlákňovania na prípravu škrobových filamentov na flexibilnú štruktúru
DE60019944T DE60019944T2 (de) 2000-12-12 2000-12-19 Elektrospinnverfahren zur Herstellung von Stärkefilamenten für flexible Strukturen
JP2000387783A JP3598313B2 (ja) 2000-12-12 2000-12-20 可撓性構造物のデンプンフィラメントを作製するための電気スピニング
CA002329289A CA2329289C (en) 2000-12-12 2000-12-20 Electro-spinning process for making starch filaments for flexible structure

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ZA200007425A ZA200007425B (en) 2000-12-12 2000-12-12 Electro-spinning process for making starch filaments for flexible structure.
NZ508818A NZ508818A (en) 2000-12-12 2000-12-12 Electro-spinning process for making starch filaments for flexible structure
AU72219/00A AU760124B2 (en) 2000-12-12 2000-12-13 Electro-spinning process for making starch filaments for flexible structure
NO20006375A NO20006375L (no) 2000-12-12 2000-12-14 Elektrospinneprosess for fremstilling av filamenter for en fleksible strukturer
SG200007497A SG93288A1 (en) 2000-12-12 2000-12-15 Electro-spinning process for making starch filaments for flexible structure
SK1963-2000A SK19632000A3 (sk) 2000-12-12 2000-12-19 Spôsob elektrozvlákňovania na prípravu škrobových filamentov na flexibilnú štruktúru
CZ20004785A CZ20004785A3 (cs) 2000-12-12 2000-12-19 Způsob elektrozvlákňování pro přípravu ąkrobových filamentů pro flexibilní strukturu
EP00127813A EP1217107B1 (de) 2000-12-12 2000-12-19 Elektrospinnverfahren zur Herstellung von Stärkefilamenten für flexible Strukturen
RU2000131894/04A RU2201945C2 (ru) 2000-12-12 2000-12-19 Способ электроформования крахмальных нитей для гибкой структуры
CA002329289A CA2329289C (en) 2000-12-12 2000-12-20 Electro-spinning process for making starch filaments for flexible structure
JP2000387783A JP3598313B2 (ja) 2000-12-12 2000-12-20 可撓性構造物のデンプンフィラメントを作製するための電気スピニング

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US10030078B2 (en) 2015-02-24 2018-07-24 The Procter & Gamble Company Process for molecular weight reduction of ethersuccinylated polysaccharides

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ZA200007425B (en) 2002-09-25
JP3598313B2 (ja) 2004-12-08
ATE294882T1 (de) 2005-05-15
CZ20004785A3 (cs) 2002-10-16
AU760124B2 (en) 2003-05-08
AU7221900A (en) 2002-06-20
NO20006375L (no) 2002-06-17
SK19632000A3 (sk) 2002-07-02
EP1217107A1 (de) 2002-06-26
ES2241543T3 (es) 2005-11-01
CA2329289A1 (en) 2002-06-20
SG93288A1 (en) 2002-12-17
DE60019944D1 (de) 2005-06-09
RU2201945C2 (ru) 2003-04-10
JP2002201531A (ja) 2002-07-19
NZ508818A (en) 2002-10-25
NO20006375D0 (no) 2000-12-14
DE60019944T2 (de) 2006-02-23

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