EP1237992A1 - Produits polymeres comprenant des compositions copolymeres polyhydroxyalcanoates souples et biodegradables et procedes de fabrication de tels produits polymeres - Google Patents

Produits polymeres comprenant des compositions copolymeres polyhydroxyalcanoates souples et biodegradables et procedes de fabrication de tels produits polymeres

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Publication number
EP1237992A1
EP1237992A1 EP00976712A EP00976712A EP1237992A1 EP 1237992 A1 EP1237992 A1 EP 1237992A1 EP 00976712 A EP00976712 A EP 00976712A EP 00976712 A EP00976712 A EP 00976712A EP 1237992 A1 EP1237992 A1 EP 1237992A1
Authority
EP
European Patent Office
Prior art keywords
product
stretching
stretched
film
copolymer
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.)
Withdrawn
Application number
EP00976712A
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German (de)
English (en)
Inventor
David Harry Melik
Isao Noda
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Procter and Gamble Co
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Procter and Gamble Co
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Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP1237992A1 publication Critical patent/EP1237992A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46—Polyesters chemically modified by esterification
    • C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/62—Compostable, hydrosoluble or hydrodegradable materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

Definitions

  • the present invention is directed to polymer products, including, but not limited to, films, fibers, nonwovens, and sheets, obtained by stretching a composition comprising a biodegradable polyhydroxyalkanoate copolymer
  • the products exhibit a desirable combination of softness and elasticity while maintaining strength
  • the products are useful for various biodegradable articles including diaper topsheets, diaper backsheets, garbage bags, food wrap, disposable garments and the like
  • Biodegradable polymers and products formed from biodegradable polymers are becoming increasingly important in view of the desire to reduce the volume of solid waste materials generated by consumers each year
  • polyhydroxyalkanoates are polyester compounds produced by a variety of microorganisms, such as bacteria and algae While polyhydroxyalkanoates have been of general interest because of their biodegradable nature, their actual use as a plastic material has been hampered by their thermal instability
  • PHB poly-3-hydroxybutyrate
  • PHB is thermoplastic and has a high degree of crystallinity and a well-defined melt temperature of about 180°C
  • PHB becomes unstable and degrades at elevated temperatures near its melt temperature Due to this thermal instability, commercial applications of PHB have been extremely limited
  • the biodegradable copolymers of Noda comprise at least two randomly repeating monomer units (RRMUs) wherein the first RRMU has the structure [-O-CH(R 1 )-(CH 2 ) n -C(O)-] wherein R 1 is H or Cl or C2 alkyl, and n is 1 or 2, and the second RRMU has the structure [-O-CH(R )-CH 2 - C(O)-] wherein R 2 is a C4-C19 alkyl or alkenyl, and wherein at least 50% of the RRMUs have the structure of the first RRMU
  • RRMUs randomly repeating monomer units
  • PHA copolymers consisting essentially of the repeat units having relatively long alkyl pendant groups of three to nine carbons, such as polyhdroxyoctanoate, are known to exhibit soft and rubber-like elasticity with some level of strength (See for example, K D Gagnon, R W Lenz, R J Farns, and R C Fuller, Macromolecules, vol 25, pp 3723-3728, 1992 )
  • the utility of soft and elastic products made of such PHA copolymers is severely limited by the disappointingly low melt temperature around 60 °C
  • the dimensional stability of the product is compromised even at a temperature of a warehouse in summer which can reach above 80 C C
  • a biodegradable soft and elastic product made of polymers having a higher melt temperature range is desired It is often desirable to stretch thermoplastic polymers in order to alter their physical properties
  • PHB and PHBV form brittle products that typically break even when drawn to only a very small extent Various methods have been attempted to improve the stretching processes and
  • the invention is directed to polymer products which are obtained by stretching a composition comprising a biodegradable polyhydroxyalkanoate copolymer
  • the biodegradable polyhydroxyalkanoate copolymer comprises at least two randomly repeating monomer units (RRMUs)
  • the first RRMU has the structure (I)
  • the copolymer further comprises a third randomly repeating unit having the structure (III)
  • Suitable polymer products include, but are not limited to, films, sheets, fibers, nonwovens, and products formed by bonding a plurality of fibers, for example nonwoven sheets and the like
  • the polymer products of the invention are advantageous in that they exhibit a combination of softness and elasticity while maintaining strength
  • the invention is directed to methods of forming improved biodegradable polymer products
  • the methods comprise stretching a composition comprising a biodegradable polyhydroxyalkanoate copolymer at a temperature above the glass transition temperature T g of the composition and below the melting temperature T m of the composition
  • the biodegradable polyhydroxyalkanoate copolymer comprises at least two RRMUs, wherein the first RRMU has the structure of formula (I) and the second RRMU has the fromula (II) as defined above
  • the copolymer further comprises a third RRMU, wherein the third R-RMU is different from the first RRMU and has the structure of formula (III), as defined above
  • At least about 70 mole % of the copolymer comprises RRMUs having the structure of the first RRMU of formula (I)
  • the methods of the invention comprise relatively easy steps as compared with many of the cumbersome methods of the prior art for producing stretched polymer products, and provide stretched polymer products having an advantageous combination of physical properties
  • the stretching process to some degree, orients the copolymer chains of the products according to the invention
  • the stretched polymer products of the invention unexpectedly exhibit an advantageous combination of physical properties, and particularly exhibit softness and elasticity while maintaining strength
  • the stretched polymer products of the invention exhibit both a higher strength, for example as measured by a higher tensile stress at break, and a higher softness, for example as measured by a lower tensile modulus, as compared with an unstretched product of the same composition
  • This combination of properties is a highly unexpected outcome of a stretching process
  • a stretching process results in products that are both stronger and stiffer (less soft), not stronger and softer
  • M S M Mark describes in Polymer Science Dictionary.
  • the stretched polymer products are formed from a composition comprising a biodegradable polyhydroxyalkanoate copolymer comprising at least two RRMUs
  • the first RRMU has the structure (I)
  • R 1 is H, or Cl or C2 alkyl, and n is 1 or 2
  • R 1 is a methyl group (CH 3 ), whereby the first RRMU has the structure
  • the second RRMU included in the biodegradable polyhydroxyalkanoate copolymer has the structure (II)
  • R 2 is a C3-C19 alkyl or C3-C19 alkenyl
  • R 2 is a C3-C15 alkyl group or alkenyl group
  • R 2 is a C3-C9 alkyl group
  • R 2 is a C5 alkyl group
  • R is a C15- C19 alkyl or alkenyl group
  • the biodegradable polyhydroxyalkanoate copolymer may comprise a third RRMU having the structure (III)
  • m is from 2 to about 9, wherein the third RRMU is different from the first RRMU
  • m is from about 2 to about 5, more preferably m is about 3
  • At least about 70 mole % of the copolymer comprises RRMUs having the structure of the first RRMU of formula (I)
  • the molar ratio of the first RRMUs to the second RRMU in the copolymer is in the range of from about 70 30 to about 98 2 More preferably, the molar ratio is in the range of from about 75 25 to about 95 5, and even more preferred, the mole ratio is in the range of from about 80 20 to about 90 10
  • the polyhydroxyalkanoate copolymer suitably has a number average molecular weight of greater than about 150,000 g/mole While not intending to be bound by theory, it is believed that the combination of the second RRMU's side chain R 2 and the indicated molar amounts sufficiently decrease the crystallinity of the first RRMU to form the copolymer with
  • one or more additional RRMUs may be included Suitably, the additional RRMUs may have the structure
  • biodegradable polyhydroxyalkanoate copolymers can be synthesized by chemical or biological based methods as disclosed, for example, by Noda in U S Patent No 5,618,855, and Noda et al in U S Patent No 5,942,597, both of which are incorporated herein by reference
  • compositions preferably comprise greater than about 50 weight percent of the biodegradable polyhydroxyalkanoate copolymer, and it is preferred that the copolymer is present as a continuous phase in the composition
  • the composition may comprise the polyhydroxyalkanoate copolymer as the only polymeric component, while in yet other embodiments, one or more additional polymers or copolymers may be included in combination with the polyhydroxyalkanoate copolymer
  • the compositions may include a combination of two or more of such biodegradable polyhydroxyalkanoate copolymers, a combination of the biodegradable polyhydroxyalkanoate copolymer as defined herein, and other polyhydroxyalkanoate copolymers, and/or additional polymeric components, for example additional polyester components or the like
  • the biodegradable polyhydroxyalkanoate copolymer preferably comprises at least about 50 weight percent, more preferably at least about 60 weight percent, and even more preferably at least about 75 weight percent, of the composition
  • compositions may further include various nonpolyme ⁇ c components including, among others, nucleating agents, antiblock agents, antistatic agents, slip agents, pro-heat stabilizers, antioxidants, pro-oxidant additives, pigments, fillers and the like
  • additives may be employed in conventional amounts although, typically, such additives are not required in the composition in order to obtain the advantageous combination of softness, elasticity, and strength
  • plasticizers may be employed in the compositions in conventional amounts although again, plasticizer are typically not required in order to obtain the advantageous combination of properties discussed above
  • the upper limit of the use temperature of biodegradable polymer products which exhibit a desirable combination of softness and elasticity, while maintaining strength, may be substantially higher than room temperature, because of the relatively high melt temperature of the polymer used to fabricate such products
  • the upper limit of the use temperature of the products can exceed above 80 °C without melting or becoming excessively soft, more preferably above 100 °C, even more preferably above 120 °C
  • the polymer products may be in any physical form and typically will comprise a stretched film, sheet, fiber, or nonwoven or a product from a stretched film, sheet, fiber, or nonwoven
  • a stretched nonwoven product can be produced by stretching a nonwoven structure that has been made by conventional means including spunbonding, melt blowing, air-laying, carding, hydroentangling, or combinations of the forementioned and the like, and in which the nonwoven can be bonded by any means known in the art, including but not limited to thermal, mechanical, chemical, or adhesive bonding
  • a plurality of stretched fibers can be bonded to form a nonwoven web which can exhibit similar softness, elastic and strength properties to the previous approach
  • the stretched polymer product need not be limited to single component structures, for example, monolayer film or monofilament fibers
  • the stretched polymer products can also include various multiconstituent products, including but not limited to (1) fiber or nonwovens having side-side, sheath-core, multiple-segment, islands-in-the-sea
  • the stretched polymer products may be conveniently formed by conventional solid state stretching techniques wherein the composition is stretched at a temperature above the glass transition temperature T g of the composition and below the melting temperature T m of the composition
  • the product is obtained by solid state stretching the composition at a temperature at least 20°C above the glass transition temperature (T g + 20°C) and at least 20°C below the melting temperature (T m - 20°C) of the composition
  • T g + 20°C the glass transition temperature
  • T m - 20°C melting temperature
  • the glass transition temperature of the polyhydroxyalkanoate copolymers employed in the compositions of the invention are generally below room temperature, 1 e , less than about 25°C
  • the melting temperatures of the copolymers are greater than about 100°C
  • the level of elasticity, including the springy characteristics, strength and softness exhibited by the stretched product will be influenced by not only the stretching temperature, but also by the rate and extent of stretching, whether the stretching is carried out at a constant or variable rate of displacement, strain or stress, the type of stretching and, for films, sheets, or nonwovens, whether the stretching is uniaxial or biaxial and, if biaxial, whether the stretching steps are performed sequentially, simultaneously, or some combination thereof
  • the stretching may be conducted at a constant or variable rate of displacement, strain or stress in accordance with techniques known in the art, for example, by a tenter framing process for films, sheets, and nonwovens, such as described by J H Bnston in Plastics Films, 2 nd Edition, Longman Inc , New York (1983), pages 83-85, or for fiber products by a spinning operation with Godet rolls or filament winding, such as described by J E Mclntyre and M J Denton in Concise Encyclopedia of Polymer Science and Engineering, John
  • the stretching of films, sheets, and nonwovens may be performed uniaxially or biaxially, and, if biaxially, the stretching steps may be performed sequentially, simultaneously or any combination thereof, in accordance with techniques known in the art All of the above described methods of stretching films, sheets, and nonwovens, including uniform as well as incremental stretching processes, can be used and are within the scope of the present invention
  • the product is obtained by stretching the composition in at least one direction to an extent greater than about 50% strain from its initial unstretched state, and more preferably in at least one direction greater than about 100% strain from its initial unstretched state
  • the product is obtained by stretching the composition in at least one direction to an extent in the range from about 200% to about 1500% strain from its initial unstretched state, and more preferably in at least one direction in the range from about 300% to about 1000% strain from its initial unstretched state
  • the effective strain in each stretch direction will depend on the deformation process and geometry For example, in a uniform stretching process like fiber spinning the effective strain is determined by the drawdown ratio, which is the ratio of the velocity of the fiber exiting the Godet or stretching rolls divided by the velocity of the fiber entering the Godet or stretching rolls, and as such is proportional to the overall change in sample length
  • the stretched polymer product may be cooled to below its glass transition temperature or may be subjected to a heat- setting step where the stretched form is annealed under strain at a temperature above the glass transition temperature of the composition but below the melting temperature of the composition and typically in the range of from about T g + 20°C to about T m - 20°C.
  • the solid state stretching may be conducted using any suitable apparatus known in the art, such as discussed above.
  • suitable apparatus known in the art, such as discussed above.
  • the examples set forth below describe the use of an Instron universal testing machine, but one of ordinary skill will appreciate other apparatus which may be employed.
  • the Instron or other stretching apparatus which is employed is preferably equipped with an environmental chamber to provide a thermally controlled stretching process.
  • One skilled in the art will appreciate that the stretching conditions and the annealing conditions, if employed, can be determined for a given composition as described herein depending on the desired end use application.
  • the stretched products of the present invention are advantageous in exhibiting a good combination of softness and elasticity while maintaining strength. More specifically, the stretched polymer products of the invention exhibit (1) higher strength, for example as measured by a higher tensile stress at break, (2) higher softness, for example as measured by a lower Young's modulus, and (3) higher elasticity, for example as measured by a higher percent recovery after release of the deforming stress, as compared with an unstretched product of the same composition. In preferred embodiments, the stretched polymer products have a tensile strength of greater than about 15 MPa, as measured for example according to ASTM D882-97 for films, and preferably greater than about 20 MPa.
  • the stretched polymer products have a Young's modulus of less than about 400 MPa, as measured for example according to ASTM D882-97 for films, more preferably less than about 300 MPa, and even more preferably less than about 200 MPa.
  • the stretched polymer products exhibit elastic behavior that results in greater than about 65% recovery of the product in less than about 15 seconds when the product is elongated up to about 50%, as measured for example according to ASTM D5459-95 for films More preferably greater than about 75% recovery, and even more preferably greater than about 85% recovery
  • the stretched products are useful for comprising various biodegradable articles including disposable, environmentally benign packaging, overwrap, absorbent articles including diaper/catemenial/feminine hygiene topsheets, nonwoven cores, and backsheets, stretch films including food and pallet wrap, agricultural films, mulch film, balloons, skin packaging, stretch packaging, bags including food and garbage bags, contraceptives including condoms and diaphraghms, shrink packaging, synthetic paper, carpeting, fishing line, hospital gowns, gloves, band-aids, wound dressings, disposable garments including shirts and socks, disposable surgical drapes, sutures, mailing envelopes, and agricultural uses including row covers, bed covers, turf covers, and weed barriers
  • EXAMPLE 1 This example demonstrates uniaxial stretching of a melt extrusion cast film according to the invention Specifically, a copolymer of 3-hydroxybutyrate and 8 4 mole percent 3- hydroxyoctanoate (hereafter a PHBO copolymer) is melt extruded into cast films of varying thicknesses ranging from about 0 003 to about 0 004 inches Rectangular strips of about 1 x 4 inches are cut from the film with the long dimension parallel to the machine direction of fabrication Individual strips are placed in an Instron universal testing machine (Model 1122, Canton, MA) such that the long dimension is in the pull direction, with a test gage length of one inch The test machine is equipped with a Sintech ReNewTM 1122/R upgrade package, TestWorksTM V3 02 software for test control and analysis, and 200 lb t high low temperature pneumatic grips (model S512 01), all from MTS Systems Corp , Research Triangle Park, NC, as well as an environmental chamber, Series 3710, from MTS
  • EXAMPLE 2 This Example demonstrates uniaxial stretching of a PHBO copolymer melt spun fiber according to the invention
  • the PHBO copolymer from Example 1 is melt spun into fibers having a diameter of about 4 mm
  • Test strands about 3 inches long are cut from the PHBO fiber following the stretching procedure described in Example 1, using a stretching temperature of about 60°C and an initial strain rate of about 2 in/in-min, strands of the PHBO fiber can be elongated in excess of 1000% before failure
  • the stretched fiber strands exhibit an elastic behavior, i e , when clamped between the thumb and forefinger on each hand of a technician and then pulled apart, the fiber is easily extended and quickly returns to its original length after release This behavior demonstrates that the PHBO fiber composition is highly ductile and the stretched PHBO fiber is springy.
  • EXAMPLE 3 This Example demonstrates uniaxial stretching of a comparative melt extrusion cast film A copolymer of 3-hydroxybutyrate and 12 mole percent 3-hydroxyvalerate (hereinafter PHBV copolymer) obtained from Zeneca Bioproducts Inc (New Castle, DE) is melt extruded into a cast film having a thickness of about 0 003 inches Following the sample preparation and stretching procedure described in Example 1 for various stretch temperatures and initial strain rates, the PHBV film strips do not stretch past 10% elongation without breaking This behavior demonstrates that PHBV compositions are stiff and brittle, and generally do not form stretched polymer products EXAMPLE 4
  • This Example demonstrates uniaxial stretching of a melt extrusion cast film according to the invention
  • a copolymer of 3-hydroxybutyrate and 6 9 mole percent 3- hydroxyhexanoate (hereafter a PHBH copolymer) is melt extruded into a cast film having a thickness of about 0 002 inches
  • a stretching temperature of about 60°C and an initial strain rate of about 4 in/in-min film strips of the PHBH cast film can be extended beyond 400% elongation before failure
  • the stretched strips exhibit an elastic behavior, i e , when clamped between the thumb and forefinger on each hand of a technician and then pulled apart, the film is easily extended to 1 5 times its original length and quickly returns to its original length after release
  • This behavior demonstrates the PHBH composition is ductile and the stretched PHBH film composition is springy
  • EXAMPLE 5 This Example demonstrates uniaxial stretching of another melt extrusion cast film according to the invention
  • a copolymer of 3-hydroxybutyrate and 9 7 mole percent 3- hydroxyoctadecanoate (hereafter a PHBOd copolymer) is melt extruded into cast films of varying thicknesses ranging from about 0 002 to about 0 005 inches
  • film strips of PHBOd cast film can be extended beyond 1000% elongation before failure
  • the stretched strips exhibit an elastic behavior, i e , when clamped between the thumb and forefinger on each hand of a technician and then pulled apart, the film is easily extended to 1.5 times its original length and quickly returns to its original length after release
  • This behavior demonstrates that the PHBOd composition is highly ductile and the stretched PHBOd film composition is springy
  • EXAMPLE 6 This Example demonstrates biaxial stretching of a PHBO melt extrusion cast film according to the invention
  • a film strip of the PHBO copolymer cast film from Example 1 is first stretched about 300% according to the procedure described in Example 1 at a temperature of about 60°C and an initial strain rate of about 4 in/in-min
  • This stretched sample is then rotated ninety degrees within the test machine such that the first stretch direction is perpendicular to the pull direction
  • a second stretch of about 300% elongation is carried out a temperature of about 60°C and an initial strain rate of about 4 in in-min
  • the springy nature of the resulting biaxially oriented film is readily discerned by simply stretching the film by hand, as the film quickly returns to its original length after release of the deforming strain
  • EXAMPLE 7 This Example compares tensile properties of stretched and unstretched PHBO melt extrusion cast films Specifically, the tensile properties of stretched and unstretched PHBO melt extruded cast film strips from Example 1 are determined by a method outlined in ASTM D882-97 using an Instron universal testing machine such as described in Example 1 The stretched samples are produced at a stretch temperature of about 60°C and an initial strain rate of about 100 in/in-min The stretched films are stronger, as evidenced by a higher stress at break, softer, as evidenced by a lower Young's modulus, but less extensible, as evidenced by a lower strain at break, than the unstretched counterparts
  • EXAMPLE 8 This Example demonstrates the elastic recovery of a stretched PHBO melt extrusion cast film according to the invention
  • the elastic properties of a stretched PHBO cast film from Example 1 are measured by determining the dimensional recovery exhibited by a film when it is stretched in an Instron universal testing machine, such as described in Example 1
  • the stretched films are prepared at a stretch temperature of about 60°C and an initial strain rate of about 100 in/in-min
  • the stretched films are extended at ambient temperature to a predetermined extension at an initial strain rate of 1 0 in/in-min, the applied stress removed, and the decrease in strain measured after about 10-15 seconds relaxation time
  • the stretched PHBO film strips show a short-term recovery of greater than about 85% from up to about 100% extension This behavior demonstrates the long-range mechanical elasticity of the products according to the invention
  • EXAMPLE 9 This Example demonstrates an elastic, pliable band-aid formed from stretched PHBO cast film according to the invention
  • a stretched film is prepared from a PHBO cast film of Example 1, where the stretching process is carried out at a temperature of about 60°C and an initial strain rate of about 20 in/in-min
  • a 0 75 x 3 inch film strip is cut from the stretched PHBO film
  • An absorbent pad 0 75 x 1 0 inch is glued lengthwise to the center of the strip, and self-adhering Velcro pieces are attached to the ends to form a band-aid
  • Use of the band-aid on an index finger shows that the film easily flexes, and follows both the back-and-forth and bending motions of the index finger without sagging
  • EXAMPLE 10 This Example demonstrates the fabrication of a springy, soft nonwoven sheet from stretched PHBO fiber according to the present invention
  • a nonwoven sheet is prepared from stretched PHBO fibers Melt spun PHBO fibers are stretched as described in Example 2 at a temperature of about 60°C and an initial strain rate of about 3 0 in/in-min Several of the stretched strands are cut to 3 inch lengths and placed randomly between two 10 mm think, 6 x 6 inch sheets of polytetrafluoroethylene (Teflon®), the whole being placed between the platens of a Carver® hydraulic laboratory press The upper platen is preheated to about 15°C above the calorimetrically determined melting point of the PHBO, and has a equally spaced spot bonding pattern of 25 1 0 mm diameter bonds per square inch Sufficient pressure is applied so as to cause the bond spots to soften and fuse The pressure is released and the nonwoven sheet is allowed to cool to room temperature before removing the outer polytetrafluoroethylene sheets
  • EXAMPLE 11 The Example demonstrates uniaxial stretching of conventional melt extrusion cast films and tensile properties thereof
  • Melt extruded cast films are made from several biodegradable polymers including polycaprolactone (Tone® P787, Union Carbide,), Bionolle 1001 and 3001 (Showa Highpolymer Co , LTD , Tokyo, JP), Eastar 14766 (Eastman Chemical Company, Kingsport, TN), and BAK 1095 (Bayer Corporation, Pittsburgh, PA), as well as from several nondegradable polymers including polypropylene (type 7300KF, Millennium Petrochemicals, Cincinnati, OH), high density polyethylene (HDPE) (type LTPR059, Millennium Petrochemicals, Cincinnati, OH), and a 50 50 by weight low density polyethylene (LDPE) linear low density polyethylene (LLDPE) blend (type NA940000 and GA5010110, respectively, Millennium Petrochemicals, Cincinnati, OH) Following the sample preparation and stretching procedure described in Example 1, using a stretching temperature of
  • the tensile properties of the stretched melt extruded cast film strips are determined by the method outlined in ASTM 882-97 using an Instron universal testing machine such as described in Example 1 Typical of stretching processes, the various stretched films are stronger, as evidenced by higher stress at break, but stiffer, as evidenced by higher Young's modulus, and less extensible, as evidenced by lower stress at break, than the unstretched counterparts
  • EXAMPLE 12 This example demonstrates the fabrication of a nonwoven sheet using a melt blown process
  • the PHBO copolymer from Example 1 is fed into an extruder which gradually melts the polymer as it feeds the melt blowing die
  • the die meters the polymer into a balancing channel that is oriented linearly in the cross machine direction and that narrows to a spinneret of several holes per linear inch
  • the fibers that are formed are continuous and extremely fine, and are blown onto a moving collector screen to form the nonwoven web structure
  • the web is thermally bonded by passing the web through a 2-roll stainless steel stack roll on which one roll there is a spot bonding pattern of about 25 1 0 mm diameter bonds per square inch
  • the stack rolls are preheated to about 15°C above the calo ⁇ met ⁇ cally determined melting point of the PHBO composition, and sufficient pressure is applied to the web as it passes through the stack roll so as to cause the spot bonds to soften and fuse
  • the stack rolls are preheated to about 15
  • EXAMPLE 13 This example demonstrates the fabrication of a springy nonwoven sheet from a melt blown nonwoven web Rectangular strips of about 1 x 4 inches are cut from the bonded PHBO web described in Example 12, with the long dimension parallel to the machine direction of fabrication Following the stretching procedure described in Example 1, using a stretching temperature of about 60°C and an initial strain rate of about 1 in/in-min, elongated strips of the PHBO nonwoven web can be produced
  • the springy nature of the stretched nonwoven sheet is readily discerned by simply stretching the sheet by hand, as the sheet is easily elongated and quickly returns to it original dimensions after release of the applied strain Comparing this behavior with that of Example 10 shows that similar springy nonwoven products can be produced by either stretching a nonwoven sheet made by conventional means or by fabricating a nonwoven sheet from stretched fibers
  • EXAMPLE 14 This example demonstrates the fabrication of a springy film product by incrementally stretching a PHBO film in a ring rolling operation according to U S Patent 4,116,892
  • the melt extruded PHBO cast film from Example 1 is introduced in the machine direction of manufacture through a pair of grooved rolls that are preheated to a temperature of about 60°C
  • the grooves are perpendicular to the machine direction of the film, have an approximate sinusoidal shape 3 mm deep and 3 mm apart, and produce a draw ratio of about 2
  • 8 groove tips simultaneously engage the film
  • the film is introduced into the nip of the intermeshing grooved rolls rotating at about 2 RPM to produce a feed velocity of approximately 2 feet per minute, and wound at about 4 feet per minute
  • the film has relatively transparent lines at 3 mm intervals corresponding to the contact points, or stretched areas, with undrawn opaque sections in between
  • the springy nature of the ring-rolled PHBO film is readily discerned in directions parallel to the machine direction by
  • EXAMPLE 15 This example demonstrates the fabrication of a stretched film product by incrementally stretching a film of Bionolle 3001 (Showa Highpolymer Co , LTD , Tokyo, JP) in a ring rolling operation Specifically, a melt extruded cast film of Bionolle 3001 with a thickness of about 0 002 inches is ring rolled according to the procedure described in Example 14, using a grooved roll temperature of about 25°C The lack of springiness is readily discerned by simply stretching the ring rolled film product by hand in directions parallel and perpendicular to the machine direction of manufacture, as the film does not easily elongate and does not return to its original dimensions after release of the applied strain In fact, the ring rolling operation permanently deforms the Bionolle 3001 film in the machine direction
  • EXAMPLE 16 This example demonstrates the fabrication of a contractive film product by incrementally stretching a multilayer film in a ring rolling operation Specifically, the PHBO copolymer from Example 1 is coextruded with the Bionolle 3001 resin from Example 15 into a two- layer cast film product where the thickness of the PHBO layer is about 0.002 inches and the Bionolle 3001 layer is about 0.001 inches. This PHBO/Bionolle film is then ring rolled according to the procedure described in Example 14, using a grooved roll temperature of about 60°C.
  • the result of the ring rolling operation is a contractive film product, in which the PHBO layer is springy as described in Example 14 and the Bionolle 3001 layer is nonspringy and permanently deformed as described in Example 15, and in which the Bionolle layer forms gathers or pleats as the PHBO layer contracts upon release of an applied strain. Additionally, the Bionolle layer limits the extent to which the product is rendered elastically extensible, at least up to the point of initial stretching.
  • EXAMPLE 17 This example demonstrates the fabrication of a disposable baby diaper, where the dimensions listed are intended for use with a child in the 6-10 kilogram size range. These dimensions can be modified proportionally for different size children, or for adult incontinence briefs, according to standard practice.
  • Backsheet 0.020-.038 mm film consisting of the PHBO copolymer from Example 1; width at top and bottom 33 cm; notched inwardly on both sides to a width-at- center of 28.5 cm; length 50.2 cm.
  • Topsheet carded and thermally bonded staple-length polyproplyene fibers (Hercules type 151 polypropylene); width at top and bottom 33 cm; nothched inwardly on both sides to a width-at-center of 28.5 cm; length 50.2 cm.
  • Absorbent core 28.6 g of cellulose wood pulp and 4.9 g of absorbent gelling material particles (commercial polyacrylate from Nippon Shokubai); 8.4 mm thick, calendered; width at top and bottom 28.6 cm; notched inwardly at both sides to a width- at-center of 10.2 cm; length 44.5 cm.
  • Elastic leg bands four individual rubber strips (2 per side); width 4.77 cm; length 37 cm; thickness 0.178 mm (all the foregoing dimensions being in the relaxed state).
  • the diaper is prepared in standard fashion by positioning the core material covered with the topsheet on the backsheet and gluing.
  • the elastic bands (designated “inner” and “outer”, corresponding to the bands closest to, and farthest from, the core, respectively) are stretched to ca 50 2 cm and positioned between the topsheet/backsheet along each longitudinal side (2 bands per side) of the core.
  • the inner bands along each side are positioned ca 55 mm from the narrowest width of the core (measured from the inner edge of the elastic bank) This provides a spacing element along each side of the diaper comprising the flexible topsheet/backsheet material between the inner elastic and the curved edge of the core
  • the inner bands are glued down along their length in the stretched state
  • the outer bands are positioned ca 13 mm from the inner bands, and are glued down along their length in the stretched state
  • the topsheet/backsheet assembly is flexible, and the glued-down bands contract to elasticize the sides of the diaper
  • EXAMPLE 18 The diaper of Example 17 is modified by replacing the elastic leg bands with the springy PHBO film product described in Example 1
  • EXAMPLE 19 The diaper of Example 17 is modified by replacing the elastic leg bands with the contractive film product described in Example 16

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Abstract

L'invention concerne des produits souples et élastiques obtenus par étirement d'une composition comprenant un copolymère polyhydroxyalcanoate biodégradable contenant au moins deux unités monomères se répétant de manière aléatoire. La première unité monomère présente la structure (I): dans laquelle R1 représente H, ou alkyle C1 ou C2, et n est 1 ou 2. La seconde unité monomère présente la structure (II): dans laquelle R2 est un alkyle C3-C19 ou un alcényle C3-C19. Au moins environ 70 % en mole du copolymère comprennent des unités monomères se répétant de manière aléatoire présentant la structure de la première unité monomère susmentionnée (I). Les produits présentent des combinaisons avantageuses de souplesse et d'élasticité tout en conservant leur résistance.
EP00976712A 1999-10-28 2000-10-27 Produits polymeres comprenant des compositions copolymeres polyhydroxyalcanoates souples et biodegradables et procedes de fabrication de tels produits polymeres Withdrawn EP1237992A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US16196999P 1999-10-28 1999-10-28
US161969P 1999-10-28
PCT/US2000/029884 WO2001030892A1 (fr) 1999-10-28 2000-10-27 Produits polymeres comprenant des compositions copolymeres polyhydroxyalcanoates souples et biodegradables et procedes de fabrication de tels produits polymeres

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EP1237992A1 true EP1237992A1 (fr) 2002-09-11

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EP (1) EP1237992A1 (fr)
JP (1) JP2003513130A (fr)
KR (1) KR20020040916A (fr)
CN (1) CN1235951C (fr)
AU (1) AU1444701A (fr)
BR (1) BR0015092A (fr)
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US6821612B1 (en) 1999-10-28 2004-11-23 The Procter & Gamble Company Methods for preparing soft and elastic biodegradable polyhydroxyalkanoate copolymer compositions and polymer products comprising such compositions
AU6977901A (en) * 2000-06-09 2001-12-17 Procter & Gamble Biodegradable coated substrates
US6903053B2 (en) 2000-06-09 2005-06-07 The Procter & Gamble Company Agricultural items and agricultural methods comprising biodegradable copolymers
AU2001268301B2 (en) * 2000-06-09 2005-08-18 The Procter & Gamble Company Agricultural items and methods comprising biodegradable copolymers
WO2003070450A1 (fr) * 2002-02-21 2003-08-28 Riken Film d'acide polyhydroxyalcanoique haute resistance et procede de production associe
BR0315787A (pt) 2002-11-08 2005-09-13 Kaneka Corp Dispersão aquosa de poliéster biodegradável e processo para preparo do mesmo
JP2005162884A (ja) * 2003-12-03 2005-06-23 Kaneka Corp ポリ（３−ヒドロキシアルカノエート）組成物を用いたフィルム
JP7222923B2 (ja) * 2018-01-22 2023-02-15 株式会社カネカ 不織布の製造方法
KR20230097008A (ko) 2020-10-26 2023-06-30 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 생체흡수성 섬유상 의료재료

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JPH06500818A (ja) * 1990-09-11 1994-01-27 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー ポリヒドロキシ酸を含有するフィルム
ID23491A (id) * 1994-01-28 1995-09-07 Procter & Gamble Kopolimer-kopolimer yang dapat dibiodegradasi dan baha-bahan plastik yang terdiri dari kopolimer-kopolimer yang dapat dibiodegradasi
ES2251716T3 (es) * 1994-01-28 2006-05-01 THE PROCTER & GAMBLE COMPANY Copolimeros biodegradables y articulos de plastico que comprenden copolimeros biodegradables de 3-hidroxihexanoato.
EP0736563A1 (fr) * 1995-04-07 1996-10-09 SAFTA S.p.A. Procédé de préparation de films complètement biodegradable avec des caractéristiques mécaniques améliorés, produits obtenus et leurs applications
GB9526165D0 (en) * 1995-12-21 1996-02-21 Zeneca Ltd Oriented polyester
JPH10147653A (ja) * 1996-11-20 1998-06-02 Gunze Ltd 微生物分解性延伸フィルム
US6174990B1 (en) * 1998-12-21 2001-01-16 The Procter & Gamble Company Films comprising biodegradable PHA copolymers

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CA2387073C (fr) 2007-03-27
CA2387073A1 (fr) 2001-05-03
BR0015092A (pt) 2002-07-16
AU1444701A (en) 2001-05-08
KR20020040916A (ko) 2002-05-30
CN1235951C (zh) 2006-01-11
JP2003513130A (ja) 2003-04-08
WO2001030892A1 (fr) 2001-05-03

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