EP1470273B1 - Nichtthermoplastische stärkefasern und stärkezusammensetzung und verfahren zu ihrer herstellung - Google Patents
Nichtthermoplastische stärkefasern und stärkezusammensetzung und verfahren zu ihrer herstellung Download PDFInfo
- Publication number
- EP1470273B1 EP1470273B1 EP03707597A EP03707597A EP1470273B1 EP 1470273 B1 EP1470273 B1 EP 1470273B1 EP 03707597 A EP03707597 A EP 03707597A EP 03707597 A EP03707597 A EP 03707597A EP 1470273 B1 EP1470273 B1 EP 1470273B1
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- EP
- European Patent Office
- Prior art keywords
- starch
- fiber
- fibers
- thermoplastic
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Images
Classifications
-
- 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
Definitions
- the present invention relates to non-thermoplastic fibers comprising modified starch and processes for making such fibers.
- the non-thermoplastic starch fibers can be used to make nonwoven webs and other disposable articles.
- the resulting fibrous web and therefore the fine-diameter starch fibers comprising such a web, possesses a sufficient wet tensile strength, flexibility, stretchability, and water-insolubility for a limited time (of use).
- thermoplastic starch or “thermoplastically-processable” starch compositions, described in several references herein below, may be suited for production of starch fibers having good stretchability and flexibility.
- the thermoplastic starch does not possess the required wet tensile strength which is a very important quality for such consumer-disposable articles as toilet tissue, paper towel, items of feminine protection, diapers, facial tissue, and the like.
- cross-linking may be necessary to obtain a sufficient wet tensile strength of starch fibers.
- chemical or enzymatic agents have been typically used to modify or destructurize the starch to produce a thermoplastic starch composition.
- a mix of starch and a plasticizer can be heated to a temperature sufficient to soften the resulting thermoplastic starch-plasticizer mix.
- pressure can be used to facilitate softening of the thermoplastic mix. Melting and disordering of the molecular structure of the starch granule takes place and a destructurized starch is obtained.
- the presence of plasticizers in the starch mix interferes with cross-linking of the starch and thus discourages the resulting starch fibers from acquiring a sufficient wet tensile strength.
- Thermoplastic or thermoplastically-processable starch compositions are described in several US patents, for example: US Patent Nos. 5,280,055 issued Jan. 18, 1994 ; 5,314,934 issued May 24, 1994 ; 5,362,777 issued Nov. 1994; 5,844,023 issued Dec. 1998; 6,117,925 issued Sep. 12, 2000; 6,214,907 issued Apr. 10, 2001; and 6,242,102 issued Jun. 5, 2001, all seven immediately preceding patents issued to Tomka; US Patent Nos. 6,096,809 issued Aug. 1, 2000 ; 6,218,321 issued Apr. 17, 2001 ; 6,235,815 and 6,235,816 issued on May 22, 2001, all four immediately preceding patents issued to Lorcks et al.; US Patent No.
- thermoplastic starch composition can be manufactured by mixing starch with an additive (such as a plasticizer), preferably without the presence of water as described, for example, in US 5, 362,777 referenced herein above.
- an additive such as a plasticizer
- U.S. Patent Nos. 5,516,815 and 5,316,578 to Buehler et al. relate to thermoplastic starch compositions for making starch fibers from a melt-spinning process.
- the melted thermoplastic starch composition is extruded through a spinneret to produce filaments having diameters slightly enlarged relative to the diameter of the die orifices on the spinneret (i.e., a die swell effect).
- the filaments are subsequently drawn down mechanically or thermomechanically by a drawing unit to reduce the fiber diameter.
- the major disadvantage of the starch composition of Buehler et al. is that it requires significant amounts of water-soluble plasticizers which interfere with cross-linking reactions to generate apparent peak wet tensile stress in starch fibers.
- thermoplastically processable starch compositions are disclosed in U.S. Patent No. 4,900,361, issued on August 8, 1989 to Sachetto et al. ; U.S. Patent No. 5,095,054, issued on March 10, 1992 to Lay et al. ; U.S. Patent No. 5,736,586, issued on April 7, 1998 to Bastioli et al. ; and PCT publication WO 98/40434 filed by Hanna et al. published March 14, 1997 .
- starch fibers relate principally to wet-spinning processes.
- a starch/solvent colloidal suspension can be extruded from a spinneret into a coagulating bath.
- References for wet-spinning starch fibers include U.S. Patent No. 4,139,699 issued to Hernandez et al. on February 13, 1979 ; U.S. Patent No. 4,853,168 issued to Eden et al. on August 1, 1989 ; and U.S. Patent No. 4,234,480 issued to Hernandez et al. on January 6, 1981 .
- JP 08-260,250 describes modified starch fibers manufactured from starch and an amino resin precondensate, and a method for making the same. The method includes dry spinning of an undiluted solution of starch and amino resin precondensate, followed by heat treatment.
- the starch used in this application is natural starch, such as contained in corn, wheat, rice, potatoes etc.
- the natural starch has a high weight average molecular weight - from 30,000,000 grams per mole (g/mol) to over 100,000,000 g/mol.
- the melt-rheological properties of an aqueous solution comprising such starch are ill-suited for high-speed spinning processes, such as spun-bonding or melt-blowing, for production of fine-diameter starch fibers.
- the art shows a need for an inexpensive and melt-processable starch composition that would allow one to produce fine-diameter starch fibers possessing good wet tensile strength properties and suitable for production of fibrous webs, particularly tissue-grade fibrous webs. Consequently, the present invention provides non-thermoplastic fine-diameter starch fibers having sufficient apparent peak wet tensile stress. The present invention further provides a process for making such non-thermoplastic starch fibers.
- the invention comprises a non-thermoplastic starch fiber, wherein the fiber as a whole does not exhibit a melting point.
- the fiber has an apparent peak wet tensile stress greater than about 0.2 MegaPascals (MPa), more specifically greater than about 0.5 MPa, even more specifically greater than about 1.0 MPa, more specifically greater than about 2.0 MPa, and even more specifically greater than about 3.0 MPa.
- the fiber has an average equivalent diameter of less than about 20 microns, more specifically less than about 10 microns, and even more specifically less than about 6 microns.
- the fiber can be manufactured from a composition comprising a modified starch and a cross-linking agent.
- the composition can have a shear viscosity from about 1 Pascal ⁇ Seconds to about 80 Pascal ⁇ Seconds, preferably from about 3 Pascal ⁇ Seconds to about 30 Pascal ⁇ Seconds, and more preferably from about 5 Pascal ⁇ Seconds to about 20 Pascal ⁇ Seconds, as measured at a shear rate of 3,000 sec -1 and at the processing temperature.
- the aldehyde cross-linking agent can be selected from the group consisting of formaldehyde, glyoxal, glutaraldehyde, urea glyoxal resin, urea formaldehyde resin, melamine formaldehyde resin, methylated ethylene urea glyoxal resin, and any combination thereof.
- the divalent or trivalent metal ion salt can be selected from the group consisting of calcium chloride, calcium nitrate, magnesium chloride, magnesium nitrate, ferric chloride, ferrous chloride, zinc chloride, zinc nitrate, aluminum sulfate, and any combination thereof.
- the acid catalyst can be selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, and any combination thereof.
- the invention comprises a fiber comprising from about 50% to about 99.5% by weight of modified starch, wherein the fiber as a whole does not exhibit a melting point.
- modified starch has a weight average molecular weight greater than about 100,000 (g/mol) prior to cross-linking.
- the modified starch comprises oxidized starch.
- the invention comprises a non-thermoplastic starch fiber having a salt-solution absorption capacity less than about 2 grams of salt solution per 1 gram of fiber, more specifically less than about 1 gram of salt solution per 1 gram of fiber, and still more specifically less than about 0.5 gram of salt solution per 1 gram of fiber.
- Non-thermoplastic starch composition is a material comprising starch and requiring water to soften to such a degree that the material can be brought into a flowing state, which can be shaped as desired, and more specifically, processed (for example, by spinning) to form a plurality of non-thermoplastic starch fibers suitable for forming a flexible fibrous structure.
- the non-thermoplastic starch composition cannot be brought into a required flowing state by the influence of elevated temperatures alone.
- non-thermoplastic starch composition may include some amounts of other components, such as, for example, plasticizers, that can facilitate flowing of the non-thermoplastic composition, these amounts by themselves are not sufficient to bring the non-thermoplastic starch composition as a whole into a flowing state in which it can be processed to form suitable non-thermoplastic fibers.
- the non-thermoplastic starch composition also differs from a thermoplastic composition in that once the non-thermoplastic composition is dewatered, for example, by drying, to comprise a solidified state, it loses its "thermoplastic" qualities. When the composition comprises a cross-linker, the dewatered composition becomes, in effect, a cross-linked thermosetting composition.
- a product such as, for example, a plurality of fibers made of such a non-thermoplastic starch composition, does not, as a whole, exhibit a melting point and does not, as a whole, have a melting temperature (characteristic of thermoplastic compositions); instead, the non-thermoplastic starch product, as a whole, decomposes without ever reaching a flowing state as its temperature increases to a certain degree ("decomposition temperature").
- a thermoplastic composition retains its thermoplastic qualities regardless of the presence and absence of water therein and can reach its melting point (“melting temperature”) and become flowable as its temperature increases.
- Non-thermoplastic starch fiber is a fiber manufactured from the non-thermoplastic starch composition.
- the non-thermoplastic starch fiber comprises a thin, slender, and flexible structure.
- the non-thermoplastic starch fiber does not exhibit a melting point and decomposes as the temperature rises, without reaching a flowable state, i. e., the state in which the fiber as a whole melts and flows so that it loses its "fiber” characteristics, such as fiber integrity, dimensions (diameter and length), etc.
- the expression “as a whole” in the present context is meant to emphasize that the fiber as an integrated element (as opposed to its separate chemical components) is under consideration.
- Fiber-diameter starch fiber is a non-thermoplastic starch fiber having an average equivalent diameter less than about 20 microns, and more specifically less than about 10 microns.
- Equivalent diameter is used herein to define a cross-sectional area of an individual non-thermoplastic fiber of the present invention, which cross-sectional area is perpendicular to the longitudinal axis of the fiber, regardless of whether this cross-sectional area is circular or non-circular.
- the fiber's cross-sectional area S of 0.005 square microns having a rectangular shape can be expressed as an equivalent circular area of 0.005 square microns, wherein the circular area has a diameter "D.”
- the diameter D is the equivalent diameter of the hypothetical rectangular cross-section.
- the equivalent diameter of the fiber having a circular cross-section is this circular cross-section's real diameter.
- "Average" equivalent diameter is an equivalent diameter computed as an arithmetic average of the actual fiber's diameter measured with an optical microscope at at least 3 positions of the fiber along the fiber's length.
- Modified starch is a starch that has been modified chemically or enzymatically.
- the modified starch is contrasted with a native starch, which is a starch that has not been modified, chemically or otherwise, in any way.
- Poly-functional chemical cross-linking reactive agents are chemical substances that have two or more chemical functional groups capable of reacting with hydroxy- or carboxy- functional groups of starch.
- the term “poly-functional chemical cross-linking reactive agents” includes di-functional chemical reactive agents.
- Embryonic non-thermoplastic starch fibers or simply “embryonic fibers” are non-thermoplastic starch fibers being manufactured at the earliest phase of their formation, existing primarily within an attenuation zone. As the embryonic fibers attenuate and are thereafter dewatered, they become non-thermoplastic fibers of the present invention. Because the embryonic fibers are an earlier phase of the resultant non-thermoplastic starch fibers being made, for reader's convenience, the embryonic fibers and the non-thermoplastic fibers are designated by the same numerical reference 110.
- Attenuation zone is a three-dimensional space outlined by an area formed by an overall shape of a plurality of extrusion nozzles in plane view (FIGs. 3-6) and extending to an attenuation distance Z (FIGs. 2 and 9) from the nozzle tips in a general direction of the movement of the fibers being made.
- the "attenuation distance” is a distance that starts at the extrusion nozzle tips and extends in the general direction of the movement of the fibers being made, and within which distance the non-thermoplastic embryonic fibers being produced are capable of attenuating to form resultant non-thermoplastic fibers having individual average equivalent diameters of less than about 20 microns.
- Processing Temperature means the temperature of the non-thermoplastic starch composition, at which temperature the non-thermoplastic starch composition of the present invention can be processed to form embryonic non-thermoplastic starch fibers.
- the processing temperature can be from 50° C to 95° C as measured at the extrusion nozzle tips.
- Salt-solution absorption capacity of a starch sample is a ratio of grams of salt solution absorbed by a starch sample per grams of starch sample, as described in TEST METHODS AND EXAMPLES below.
- “Apparent Peak Wet Tensile Stress,” or simply “Wet Tensile Stress,” is a condition existing within a non-thermoplastic starch fiber at the point of its maximum (i.e., “peak") stress as a result of strain by external forces, and more specifically elongation forces, as described in TEST METHODS AND EXAMPLES below.
- the stress is "apparent” because a change, if any, in the fiber's diameter resulting from the fiber's elongation, is not taken into consideration for the purposes of the test.
- the apparent peak wet tensile stress of the non-thermoplastic fibers is proportional to their wet tensile strength and is used herein to quantitatively estimate the latter.
- Non-thermoplastic starch fibers 110 (FIGs. 1, 7-9, and 10) of the present invention can be produced from a composition comprising a modified starch and a cross-linking agent.
- the composition may comprise from about 50% to about 75% by weight of modified starch, from about 0.1% to about 10% by weight of an aldehyde cross-linking agent, and from about 25% to about 50% by weight of water.
- Such a composition can beneficially have a shear viscosity from about 1 Pascal ⁇ Seconds (Pa ⁇ s) to about 80 Pa ⁇ s, as measured at a shear rate of 3,000 sec -1 and at the processing temperature.
- non-thermoplastic starch composition herein may comprise from about 50 % to about 75 % by weight of the modified starch.
- the composition may further have an apparent extensional viscosity from about 150 Pa ⁇ s to about 13,000 Pa ⁇ s, as measured at an extension rate of about 90 sec -1 and the processing temperature.
- the extensional viscosity and the shear viscosity can be measured according to TEST METHODS described herein.
- a natural starch can be modified chemically or enzymatically, as well known in the art.
- the natural starch can be acid-thinned, hydroxy-ethylated or hydroxy-propylated or oxidized.
- the present invention can be beneficially practiced with high amylopectin natural starches derived from agricultural sources, which offer the advantages of being abundant in supply, easily replenishable and inexpensive.
- Chemical modifications of starch typically include acid or alkali hydrolysis and oxidative chain scission to reduce molecular weight and molecular weight distribution.
- Suitable compounds for chemical modification of starch include organic acids such as citric acid, acetic acid, glycolic acid, and adipic acid; inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, and partial salts of polybasic acids, e.g., KH 2 PO 4 , NaHSO 4 ; group Ia or IIa metal hydroxides such as sodium hydroxide, and potassium hydroxide; ammonia; oxidizing agents such as hydrogen peroxide, benzoyl peroxide, ammonium persulfate, potassium permanganate, hypochloric salts, and the like; and mixtures thereof.
- organic acids such as citric acid, acetic acid, glycolic acid, and adipic acid
- inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, and partial salts of polybasic acids, e.g., KH 2 PO 4 , NaHS
- Chemical modifications may also include derivatization of starch 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 can be used as 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.
- Biological modifications of starch may include bacterial digestion of the carbohydrate bonds, or enzymatic hydrolysis using enzymes such as amylase, amylopectase, and the like.
- Suitable naturally occurring starches can include, but are not limited to: com starch, potato starch, sweet potato starch, wheat starch, sago palm starch, tapioca starch, rice starch, soybean starch, arrow root starch, amioca starch, bracken starch, lotus starch, waxy maize starch, and high amylose corn starch.
- Naturally occurring starches, particularly corn starch and wheat starch can be particularly beneficial due to their low cost and availability.
- the cross-linking agent that can be used in the present invention comprises a poly-functional chemical reactive agent capable of reacting with hydroxy-functional groups or carboxy functional groups of the modified starch.
- Cross-linking agents used in the paper industry to cross-link wood pulp fibers are generally termed "wet-strength resins.” These wet-strength resins can be also useful in cross-linking starch-based materials.
- Polyamide-epichlorohydrin resins are cationic polyamide amine-epichlorohydrin wet-strength resins that have been found to be of particular utility. Suitable types of such resins are described in U.S. Patent Nos. 3,700,623, issued on October 24, 1972 , and 3,772,076, issued on November 13, 1973 , both issued to Keim and both being hereby incorporated by reference herein for the purpose of describing types of the wet-strength resins that can be used in the present invention.
- One commercial source of a useful polyamide-epichlorohydrin resin is Hercules Inc. of Wilmington, Delaware, which markets such resins under the name Kymene®.
- 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. , both patents being incorporated herein by reference for the purpose of describing types of the wet-strength resins that can be used in the present invention.
- One commercial source of glyoxylated polyacrylamide resins is Cytec Co. of Stanford, CT, which markets one such resin under the name Parez ® 631 NC.
- non-thermoplastic starch fibers produced from the non-thermoplastic starch composition have a significant wet tensile strength that can be appreciated by testing the fibers' apparent peak wet tensile stress, as described below. Consequently, products, such as, for example, fibrous webs suitable for consumer-disposable items, produced with the non-thermoplastic starch fibers of the present invention will also have a significant apparent peak wet tensile stress.
- Still other cross-linking agents finding utility in this invention include divinyl sulphone, anhydride containing copolymers, such as styrene-maleic anhydride copolymers, dichloroacetone, dimethylolurea, diepoxides such as bisepoxybutane or bis(glycidyl ether), epichlorohydrin, and diisocyanates.
- divalent and trivalent metal ions are useful in the present invention for cross-linking starch by formation of metal ion complexes with carboxy functional groups on starch.
- oxidized starches which have increased levels of carboxy functional groups, can be cross-linked well with divalent and trivalent metal ions.
- polycationic polymers from either natural or synthetic sources are also useful for cross-linking starch by formation of ion pair complexes with carboxy functional groups on starch to form insoluble complexes commonly termed "coacervates.”
- Metal ion cross-linking has been found to be particularly effective when used in combination with covalent cross-linking reagents.
- a suitable cross-linking agent can be added to the composition in quantities ranging from about 0.1% by weight to about 10% by weight, more typically from about 0.1 % by weight to about 3% by weight.
- Natural, unmodified starch generally has a very high weight average molecular weight and a broad molecular weight distribution, e.g. natural corn starch has a weight average molecular weight greater than about 40,000,000 g/mol. Therefore, natural, unmodified starch does not have the inherent rheological properties suitable for use in high speed solution spinning processes such as spunbonding or meltblowing nonwoven processes which are capable of producing fine-diameter fibers. These small diameters are very beneficial in achieving sufficient softness and opacity of the end productimportant functional properties for a variety of consumer-disposable products, such as, for example, toilet tissue, wipes, diapers, napkins, and disposable towels.
- the molecular weight of the natural, unmodified starch must be reduced.
- the optimum molecular weight is dependent on the type of starch used.
- a starch with a low level of amylose component such as a waxy maize starch, disperses rather easily in an aqueous solution with the application of heat and does not retrograde or recrystallize significantly.
- a waxy maize starch can be used at a relatively high weight average molecular weight, for example in the range of 500,000 g/mol to 5,000,000 g/mol.
- the average molecular weight of starch can be reduced to the desirable range for the present invention by chain scission (oxidative or enzymatic), hydrolysis (acid or alkaline catalyzed), physical/mechanical degradation (e.g., via the thermomechanical energy input of the processing equipment), or combinations thereof.
- the thermomechanical method and the oxidation method offer an additional advantage in that they are capable of being carried out in situ of the melt-spinning process. It is believed the non-thermoplastic fibers of the present invention may contain from about 50% to about 99.5% by weight of modified starch.
- the natural starch can be hydrolyzed in the presence of an acid catalyst to reduce the molecular weight and molecular weight distribution of the composition.
- the acid catalyst can be selected from the group consisting of hydrochloric acid, sulfuric acid, phosphoric acid, citric acid, and any combination thereof.
- a chain scission agent may be incorporated into a spinnable starch composition such that the chain scission reaction takes place substantially concurrently with the blending of the starch with other components.
- oxidative chain scission agents suitable for use herein include ammonium persulfate, hydrogen peroxide, hypochlorite salts, potassium permanganate, and mixtures thereof.
- the divalent or trivalent metal ion salt can comprise any water-soluble divalent or trivalent metal ion salt and can be selected from the group consisting of calcium chloride, calcium nitrate, magnesium chloride, magnesium nitrate, ferric chloride, ferrous chloride, zinc chloride, zinc nitrate, aluminum sulfate, ammonium zirconium carbonate, and any combination thereof.
- the polycationic polymer can comprise any water-soluble polycationic polymer such as, for example, polyethyleneimine, quatemized polyacrylamide polymer such as Cypro® 514 manufactured by Cytec Industries, Inc, West Patterson, N.J., or natural polycationic polymers such as chitosan, and any combination thereof.
- non-thermoplastic starch fibers of the present invention generation of wet tensile strength in the non-thermoplastic starch fibers of the present invention can be achieved by reducing the weight average molecular weight of the starch to allow production of a non-thermoplastic starch composition having appropriate rheological properties for high-speed solution spinning of fine-diameter non-thermoplastic starch fibers, followed by cross-linking of the starch in the fibers being formed.
- Cross-linking increases molecular weight of the starch in the fibers being formed, thereby facilitating fibers' water-insolubility, which in turn results in a high wet tensile strength of the resultant non-thermoplastic starch fibers.
- Extensional, or elongational, viscosity ( ⁇ e ) relates to extensibility of the non-thermoplastic starch composition and can be particularly important for extensional processes such as fiber-making.
- the extensional viscosity includes three types of deformation: uniaxial or simple extensional viscosity, biaxial extensional viscosity, and pure shear extensional viscosity.
- the uniaxial extensional viscosity is important for uniaxial extensional processes such as fiber spinning, melt blowing, and spun bonding.
- the Trouton ratio (Tr) can be used to express extensional flow behavior of the starch composition of the present invention.
- the uniaxial extension Trouton ratio has a constant value of 3.
- the extensional viscosity is dependent on the deformation rate ( ⁇ •) and time (t).
- Trouton ratio may range from about 5 to about 1,000, specifically from about 30 to about 300, and more specifically from about 50 to about 200, when measured at the processing temperature and 90 sec -1 extension rate.
- the non-thermoplastic fibers of the present invention may find use in a variety of consumer-disposable articles such as nonwovens suitable for webs for tissue grades of paper such as those used in the production of toilet paper, paper towel, napkins and facial tissue toilet paper, diapers, items of feminine protection and incontinence articles, and the like.
- these fibers can be used 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, 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, 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.
- a process of making non-thermoplastic fibers according to the present invention comprises the following steps.
- Attenuation air can be provided by heating compressed air from a source 106 by an electrical-resistance heater 108, for example, a heater manufactured by Chromalox, Division of Emerson Electric, of Pittsburgh, PA, USA.
- the attenuating air had an absolute pressure from about 130 kPa to about 310 kPa, measured in the pipe 115.
- a beaker was disposed in a water bath to boil for approximately one hour while the starch mix was stirred manually to destructurize the starch and to evaporate the amount of water until about 25 grams of water remain in the breaker. Then the mixture was cooled to a temperature of about 40 °C. A portion of the mixture was transferred to a 10 cubic centimeters (cc) syringe and extruded therefrom to form a fiber. The fiber was manually elongated so that the fiber had a diameter between about 10 microns and about 100 microns. Then, the fiber was suspended in an ambient air for approximately one minute to allow the fiber to dry and solidify.
- cc cubic centimeters
- the fiber 110 can be sufficiently moistened.
- an ultrasonic humidifier (not shown) can be turned on, with a rubber hose positioned about 200 millimeters (about 8 inches) away from the fiber so as to direct the output mist directly at the fiber.
- the fiber 110 can be exposed to the vapor for about one minute, after which the force load P can be applied to the fiber 110.
- the fiber 110 continues to be exposed to the vapor during the application of the force load that imparts elongation force to the fiber 110. Care should be taken to ensure that the fiber 110 is continuously within the main stream of the humidifier output as the force is applied to the fiber.
- droplets of water are typically visible on or around the fiber 110.
- the humidifier, its contents, and the fiber 110 are allowed to equilibrate to an ambient temperature before use.
- the wet tensile stress can be calculated in units of MegaPascals (MPa).
- the test can be repeated multiple times, for example eight times.
- the results of wet tensile stress measurements of eight fibers are averaged.
- the force readings from the force transducer are corrected for the mass of the residual coupon by subtracting the average force transducer signal collected after the fiber had broken from the entire set of force readings.
- the stress at failure for the fiber can be calculated by taking the maximum force generated on the fiber divided by the cross-sectional area of the fiber based on the optical microscope measurements of the fiber's average equivalent diameter measured prior to conducting the test.
- the following method uses a Blue Dextran® solution.
- the Blue Dextran® molecules are large enough so that they do not penetrate into starch fibers or particles, while water molecules do penetrate and are absorbed by the starch fiber. Therefore, as a result of water absorption by the starch fiber, the Blue Dextran® is concentrated in the solution and can be measured precisely using an optical absorbance measurement.
- the optical absorbance of the Blue Dextran® / salt solution (a blank or baseline measurement) can be measured using a standard one-centimeter cuvette at 617 nanometers wavelength with a DR/4000U UV/VIS Spectrophotometer, manufactured by HACH Company, Loveland, Colorado, USA.
- a film of starch is prepared by "destructurizing" starch by heating 25 grams of starch with 25 grams of distilled water for approximately one hour in a glass beaker in a water bath which has been heated to 95 °C. After the starch has been destructurized, Parez® 490 cross-linker and phosphoric acid catalyst are added to the starch mixture and the mixture is stirred. The mixture is poured onto a one foot square sheet of Teflon® material and spread to form a film. The film is allowed to dry at a room temperature for one day and is then cured in an oven at about 120 °C for ten minutes.
- the dried film is broken and placed in an IKA All Basic grinder, manufactured by IKA Works, Inc., of Wilmington, NC, USA, and ground at 25,000 rpm for approximately one minute.
- the ground starch is then sieved through a 600-micron sieve, for example, a Sieve Number 30, manufactured by U.S. Standard Sieve Series, A.S.T.M E-11 Specifications, manufactured by Dual Mfg. Co., Chicago, IL, USA, onto a 300 micron sieve (Sieve Number 50).
- the die can be attached to the lower end of the barrel, which is held at a fixed test temperature t of about 75 °C, roughly corresponding to the temperature at which the non-thermoplastic starch composition is to be processed.
- the sample starch composition can be preheated to the die temperature and loaded into the barrel of the rheometer, to substantially fill the barrel. If, after the loading, air bubbles to the surface, compaction can be used prior to running the test to rid the molten sample of the entrapped air.
- a piston can be 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.
- the weight average molecular weight (Mw) of the non-thermoplastic starch can be determined by Gel Permeation Chromatography (GPC) using a mixed bed column.
- Components of a high performance liquid chromatograph (HPLC) are as follows: Pump: Millenium®, Model 600E, manufactured by Waters Corporation of Milford, MA, USA.
- Guard Column PL gel 20 ⁇ m, 50 mm length, 7.5 mm ID
- Column Heater CHM-009246, manufactured by Waters Corporation.
- Wyatt Technology's Optilab® differential refractometer set at 50 °C. Gain set at 10.
- the starch samples can be prepared by dissolving the starch into the mobile phase at nominally 3 mg of starch / 1 mL of mobile phase.
- the sample can be capped and then stirred for about 5 minutes using a magnetic stirrer.
- the sample can then be placed in an 85 °C convection oven for about 60 minutes.
- the sample then can be allowed to cool undisturbed to a room temperature.
- the sample can then be filtered through a 5 ⁇ m syringe filter (for example, through a 5 ⁇ m Nylon membrane, type Spartan-25, manufactured by Schleicher & Schuell, of Keene, NH, US), into a 5 milliliters (mL) autosampler vial using a 5 mL syringe.
- a 5 ⁇ m syringe filter for example, through a 5 ⁇ m Nylon membrane, type Spartan-25, manufactured by Schleicher & Schuell, of Keene, NH, US
- a blank sample of solvent can be injected onto the column. Then a check sample can be prepared in a manner similar to that related to the samples described above.
- the check sample comprises 2 mg/mL of pullulan (Polymer Laboratories) having a weight average molecular weight of 47,300 g/mol.
- the check sample can be analyzed prior to analyzing each set of samples. Tests on the blank sample, check sample, and non-thermoplastic starch test samples can be run in duplicate. The final run can be a third run of the blank sample.
- the light scattering detector and differential refractometer can be run in accordance with the "Dawn EOS Light Scattering Instrument Hardware Manual” and "Optilab® DSP Interferometric Refractometer Hardware Manual,” both manufactured by Wyatt Technology Corp., of Santa Barbara, CA, USA, and both incorporated herein by reference.
- the weight average molecular weight of the sample is calculated using the Astra® software, manufactured by Wyatt Technology Corp. A dn/dc (differential change of refractive index with concentration) value of 0.066 is used.
- the baselines for laser light detectors and the refractive index detector are corrected to remove the contributions from the detector dark current and solvent scattering. If a laser light detector signal is saturated or shows excessive noise, it is not used in the calculation of the molecular mass.
- the regions for the molecular weight characterization are selected such that both the signals for the 90° detector for the laser-light scattering and refractive index are greater than 3 times their respective baseline noise levels.
- the high molecular weight side of the chromatogram is limited by the refractive index signal and the low molecular weight side is limited by the laser light signal.
- Relative humidity can be measured using wet and dry bulb temperature measurements and an associated psychometric chart.
- Wet bulb temperature measurements are made by placing a cotton sock around the bulb of a thermometer. Then the thermometer, covered with the cotton sock, is placed in hot water until the water temperature is higher than an anticipated wet bulb temperature, more specifically, higher than about 82 °C (about 180 °F). The thermometer is placed in the attenuating air stream, at about 3 millimeters (about 1/8 inch) from the extrusion nozzle tips. The temperature will initially drop as the water evaporates from the sock. The temperature will plateau at the wet bulb temperature and then will begin to climb once the sock loses its remaining water. The plateau temperature is the wet bulb temperature. If the temperature does not decrease, then the water must be heated to a higher temperature.
- the dry bulb temperature is measured using a 1.6 mm diameter J-type thermocouple placed at about 3 mm downstream from the extrusion nozzle tip.
- a relative humidity can be determined. Relative Humidity can be read off the chart, based on the wet and dry bulb temperatures.
- a standard Pitot tube can be used to measure the air velocity.
- the Pitot tube is aimed into the air stream, producing a dynamic pressure reading from an associated pressure gauge.
- the dynamic pressure reading, plus a dry bulb temperature reading is used with the standard formulas to generate an air velocity.
- a 1.24 mm (0.049 inches) Pitot tube, manufactured by United Sensor Company of Amherst, NH, USA, can be connected to a hand-held digital differential pressure gauge (manometer) for the velocity measurements.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Nonwoven Fabrics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Claims (10)
- Nichtthermoplastische Stärkefaser mit einer scheinbaren Spitzen-Nasszugfestigkeit von mehr als 0,2 Megapascal (MPa), vorzugsweise mehr als 0,5 MPa, mehr bevorzugt mehr als 1,0 MPa, mehr bevorzugt mehr als 2,0 MPa und noch mehr bevorzugt mehr als 3,0 MPa, wobei die Faser zu 50 Gew.-% bis 99,5 Gew.- % eine modifizierte Stärke umfasst, wobei die modifizierte Stärke ein Molekulargewicht-Gewichtsmittel von mehr als 100.000 g/Mol vor der Vernetzung hat und die Faser einen durchschnittlichen Äquivalentdurchmesser von weniger als 20 Mikrometer hat, wobei die nichtthermoplastische Stärkefaser in der Gesamtheit keinen Schmelzpunkt hat.
- Faser nach Anspruch 1, wobei die Faser aus einer Zusammensetzung, die eine modifizierte Stärke und ein Vernetzungsmittel umfasst, hergestellt ist.
- Faser nach einem der Ansprüche 1 oder 2, wobei die Faser einen durchschnittlichen Äquivalentdurchmesser von weniger als 10 Mikrometer und vorzugsweise weniger als 6 Mikrometer hat.
- Faser nach Ansprüchen 1 - 3, wobei die Faser ein Absorptionsvermögen für Salzlösung von weniger als 2 Gramm Salzlösung pro 1 Gramm Faser, vorzugsweise weniger als 1 Gramm Salzlösung pro 1 Gramm Faser und mehr bevorzugt weniger als 0,5 Gramm Salzlösung pro 1 Gramm Faser aufweist.
- Verfahren zum Herstellen nichtthermoplastischer Stärkefasern, wobei die Faser zu 50 Gew.-% bis 99,5 Gew.-% eine modifizierte Stärke umfasst, wobei die modifizierte Stärke ein Molekulargewicht-Gewichtsmittel von mehr als 100.000 g/Mol vor der Vernetzung hat und wobei die Faser einen durchschnittlichen Äquivalentdurchmesser von weniger als 20 Mikrometer hat, wobei das Verfahren die folgenden Schritte umfasst:(a) Bereitstellen einer nichtthermoplastischen Stärkezusammensetzung, die zu 50 Gew.-% bis 75 Gew.-% modifizierte Stärke und zu 25 Gew.-% bis 50 Gew.-% Wasser umfasst und eine Scherviskosität von ungefähr 1 Pascalsekunde (Pa.s) bis 80 Pa.s bei einer Verarbeitungstemperatur und einer Schergeschwindigkeit von 3.000 s-1 aufweist;(b) Extrudieren der nichtthermoplastischen Stärkezusammensetzung durch mehrere Extrusionsdüsen, die jeweils in einer Düsenspitze enden, wodurch mehrere embryonische Stärkefasern gebildet werden, wobei die mehreren Düsen in mehreren Reihen angeordnet sind, um eine Verlangsamungszone zu bilden, die von den Düsenspitzen zu einem Streckungsabstand in einer allgemeinen Fließrichtung der nichtthermoplastischen Stärkezusammensetzung verläuft, während vorzugsweise eine relative Feuchtigkeit in der Verlangsamungszone von mehr als ungefähr 50 % bewahrt wird;(c) Bereitstellen von verlangsamender Luft mit einer relativen Feuchtigkeit von mehr als 50 %, wie an den Düsenspitzen gemessen;(d) Verlangsamen der mehreren embryonischen Fasern mit einer verlangsamenden Luft mit einer Geschwindigkeit von mehr als 30 m/s an den Düsenspitzen, wobei mehrere nichtthermoplastische Stärkefasern mit einzelnen durchschnittlichen Äquivalentdurchmessern von weniger als 20 Mikrometer erzeugt werden; und(e) Entwässern der nichtthermoplastischen Stärkefasern auf eine Konsistenz von 70 Gew.-% bis 99 Gew.-%.
- Verfahren nach Anspruch 5, wobei der Schritt des Bewahrens der relativen Feuchtigkeit in der Verlangsamungszone das Bereitstellen einer physischen Umschließung der Verlangsamungszone umfasst.
- Verfahren nach Ansprüchen 5 und 6, wobei der Schritt des Bewahrens der relativen Feuchtigkeit in der Verlangsamungszone das Bereitstellen von Begrenzungsluft, vorzugsweise mit einer Feuchtigkeit von mehr als 50 und einer Geschwindigkeit, die im Wesentlichen gleich der Geschwindigkeit der verlangsamenden Luft ist, umfasst.
- Verfahren nach Ansprüchen 5 - 7, ferner umfassend einen Schritt des Bereitstellens einer sekundären verlangsamenden Luft durch mindestens eine sekundäre Verlangsamungsluftdüse, die der verlangsamenden Luft nachgeschaltet angeordnet ist, wobei die sekundäre verlangsamende Luft vorzugsweise eine Geschwindigkeit von ungefähr 30 m/s bis ungefähr 500 m/s am Ausgang der sekundären Verlangsamungsluftdüse hat.
- Verfahren nach Anspruch 5, wobei bei dem Schritt des Bereitstellens einer nichtthermoplastischen Stärkezusammensetzung die nichtthermoplastische Stärkezusammensetzung ferner zu ungefähr 0,1 Gew.-% bis ungefähr 10 Gew.-% ein Aldehyd-Vernetzungsmittel, vorzugsweise ausgewählt aus der Gruppe, bestehend aus Formaldehyd, Glyoxal, Glutaraldehyd, Harnstoff-Glyoxalharz, Harnstoff Formaldehydharz, Melamin-Formaldehydharz, methyliertem Ethylenharnstoff-Glyoxalharz und jeglicher Kombination davon; und zu 0,1 Gew.-% bis 15 Gew.- % eine polykationische Verbindung, vorzugsweise ausgewählt aus der Gruppe, bestehend aus zweiwertigem oder dreiwertigem Metallionensalz, natürlichen polykationischen Polymeren, synthetischen polykationischen Polymeren und jeglicher Kombination davon, umfasst.
- Verfahren nach Anspruch 5, wobei bei dem Schritt des Bereitstellens einer nichtthermoplastischen Stärkezusammensetzung die nichtthermoplastische Stärkezusammensetzung ferner einen Säurekatalysator in der ausreichenden Menge zum Bereitstellen eines pH der Zusammensetzung im Bereich von 1,5 bis 5,0 umfasst, wobei der Säurekatalysator vorzugsweise ausgewählt ist aus der Gruppe, bestehend aus Salzsäure, Schwefelsäure, Phosphorsäure, Citronensäure und jeglicher Kombination davon.
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/061,680 US6811740B2 (en) | 2000-11-27 | 2002-02-01 | Process for making non-thermoplastic starch fibers |
US10/062,393 US6723160B2 (en) | 2002-02-01 | 2002-02-01 | Non-thermoplastic starch fibers and starch composition for making same |
US61680 | 2002-02-01 | ||
US62393 | 2002-02-01 | ||
PCT/US2003/002724 WO2003066942A1 (en) | 2002-02-01 | 2003-01-30 | Non-thermoplastic starch fibers and starch composition and process for making same |
Publications (2)
Publication Number | Publication Date |
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EP1470273A1 EP1470273A1 (de) | 2004-10-27 |
EP1470273B1 true EP1470273B1 (de) | 2007-11-21 |
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EP03707597A Expired - Lifetime EP1470273B1 (de) | 2002-02-01 | 2003-01-30 | Nichtthermoplastische stärkefasern und stärkezusammensetzung und verfahren zu ihrer herstellung |
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EP (1) | EP1470273B1 (de) |
JP (1) | JP4313209B2 (de) |
CN (1) | CN1292111C (de) |
AU (1) | AU2003209435B2 (de) |
BR (1) | BR0307295A (de) |
CA (1) | CA2472550C (de) |
ES (1) | ES2295560T3 (de) |
HK (1) | HK1078907A1 (de) |
MX (1) | MXPA04007377A (de) |
PL (1) | PL373419A1 (de) |
TW (1) | TW200411094A (de) |
WO (1) | WO2003066942A1 (de) |
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US7947766B2 (en) | 2003-06-06 | 2011-05-24 | The Procter & Gamble Company | Crosslinking systems for hydroxyl polymers |
US6955850B1 (en) * | 2004-04-29 | 2005-10-18 | The Procter & Gamble Company | Polymeric structures and method for making same |
US6977116B2 (en) | 2004-04-29 | 2005-12-20 | The Procter & Gamble Company | Polymeric structures and method for making same |
AU2005319271B2 (en) * | 2004-12-20 | 2009-06-11 | The Procter & Gamble Company | Polymeric structures comprising an hydroxyl polymer and processes for making same |
US20060134410A1 (en) | 2004-12-20 | 2006-06-22 | Mackey Larry N | Polymeric structures comprising an unsubstituted hydroxyl polymer and processes for making same |
US7572504B2 (en) | 2005-06-03 | 2009-08-11 | The Procter + Gamble Company | Fibrous structures comprising a polymer structure |
US7772391B2 (en) | 2005-06-16 | 2010-08-10 | The Procter & Gamble Company | Ethersuccinylated hydroxyl polymers |
CN103025410B (zh) * | 2010-07-07 | 2015-02-18 | 三菱丽阳株式会社 | 中空纤维膜的干燥装置及干燥方法 |
US8871017B2 (en) * | 2012-04-13 | 2014-10-28 | Hasbro, Inc. | Modeling compound |
EP3262080A1 (de) | 2015-02-24 | 2018-01-03 | The Procter and Gamble Company | Verfahren zur reduktion des molekulargewichts von ethersuccinylierten polysacchariden |
CN106116307A (zh) * | 2016-06-29 | 2016-11-16 | 陈建峰 | 一种高粘接干粉砂浆的制备方法 |
DE102020216545B3 (de) * | 2020-12-23 | 2022-05-12 | Friedrich-Alexander-Universität Erlangen-Nürnberg | Verfahren und Messanordnung zum Ermitteln einer Fließeigenschaft eines Fluids |
CN113882024B (zh) * | 2021-10-27 | 2022-10-14 | 扬州大学 | 静电纺丝制备淀粉纳米纤维的方法 |
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GB8602115D0 (en) * | 1986-01-29 | 1986-03-05 | Courtaulds Plc | Absorbent fibres |
NZ503232A (en) * | 1999-03-08 | 2001-11-30 | Humatro Corp | Melt processable starch compositions comprising amylopectin and a high polymer (such as polyacrylamide) |
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- 2003-01-30 ES ES03707597T patent/ES2295560T3/es not_active Expired - Lifetime
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- 2003-01-30 TW TW092102211A patent/TW200411094A/zh unknown
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Publication number | Publication date |
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CA2472550C (en) | 2008-04-15 |
ES2295560T3 (es) | 2008-04-16 |
TW200411094A (en) | 2004-07-01 |
JP4313209B2 (ja) | 2009-08-12 |
WO2003066942A1 (en) | 2003-08-14 |
EP1470273A1 (de) | 2004-10-27 |
JP2006503988A (ja) | 2006-02-02 |
BR0307295A (pt) | 2004-12-21 |
CN1292111C (zh) | 2006-12-27 |
AU2003209435B2 (en) | 2006-05-11 |
AU2003209435A1 (en) | 2003-09-02 |
HK1078907A1 (en) | 2006-03-24 |
CN1625615A (zh) | 2005-06-08 |
MXPA04007377A (es) | 2004-11-26 |
CA2472550A1 (en) | 2003-08-14 |
PL373419A1 (en) | 2005-08-22 |
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