WO1997022459A1 - Oriented polyester - Google Patents

Oriented polyester Download PDF

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Publication number
WO1997022459A1
WO1997022459A1 PCT/US1996/020546 US9620546W WO9722459A1 WO 1997022459 A1 WO1997022459 A1 WO 1997022459A1 US 9620546 W US9620546 W US 9620546W WO 9722459 A1 WO9722459 A1 WO 9722459A1
Authority
WO
WIPO (PCT)
Prior art keywords
pha
stretching
preform
temperature
time
Prior art date
Application number
PCT/US1996/020546
Other languages
French (fr)
Inventor
Paul Waldock
Original Assignee
Monsanto Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Monsanto Company filed Critical Monsanto Company
Priority to JP9523041A priority Critical patent/JP2000502298A/en
Priority to AU13467/97A priority patent/AU1346797A/en
Priority to EP96945000A priority patent/EP0868287A1/en
Publication of WO1997022459A1 publication Critical patent/WO1997022459A1/en

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • 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

  • This invention relates to oriented polyester and in particular to oriented shaped articles made of stereospecific polyhydroxyalkanoate (PHA).
  • PHA stereospecific polyhydroxyalkanoate
  • EP-A-0104731 describes a process of making oriented shaped articles, specifically fibre but possibly others such as film, by extruding a preform, effecting a controlled degree of crystallisation, drawing the article and increasing its degree of crystallinity. Such a process, while effective, is difficult to control and inconvenient if it is desired to change line speed.
  • a process of producing an oriented PHA article comprises: (a) melting PHA; (b) shaping preform therefrom;
  • step (d) stretching the preform to cause orientation of the PHA is characterised by: between steps (b) and (c) stretching the preform before it has fully solidified.
  • the stretch between steps (b) and (c) will be referred to as "first stretch” and the stretch in step (d) as "second stretch.”
  • the first stretch takes place at a temperature less than the melting point of the PHA typically by 5-20°C, but by not more than 60°C.
  • the temperature profile of the article is controlled to afford the required extent of first stretch. Conveniently this is effected by a current of gas, especially air, at a suitable temperature and flow rate.
  • steps (b) and (c) and of first stretch are controlled to bring the preform to a level of crystallinity sufficient to avoid adhesion between PHA layers or between a PHA layer and a guiding surface such as a roller.
  • first stretch is incomplete to permit further stretching in step (d) and is, in any event, limited by what is practicable in the incompletely solid condition of the PHA and the fact that it is not accompanied by significant orientation. Typically it is by a factor in the range
  • First stretch may be in the machine direction or transverse direction or both.
  • the preform is a tube and is flattened after solidification; and the first stretch is effected by pressure of fluid, suitably applied coaxially of the extrusion die and contained by the closed end of the tube between flattening rolls.
  • Typical extents of first stretch are in the range 5 to 10 (machine direction) and 2 to 5 (transverse).
  • the first stretched preform can be passed to step (d) immediately or after a convenient period, which can be up to 10 minutes but possibly longer depending on process conditions.
  • Step (d) is effected by techniques differing according to the shape of the article being made.
  • a suitable draw ratio is at least 3, for example in the range 5 to 8.
  • transverse stretching is practised, using stenter clamps applied to the sides of the advancing film.
  • transverse stretching may be by compressed gas.
  • tube formed in step (b) may be slit to flat film before step (d) or before heating step for step (d).
  • the temperature at which step (d) stretching is effected is preferably within 60 to 1 10°C of the PHA melting point.
  • the degree of stretch in step (d) is preferably in the range 60-80% of the maximum possible, so as to provide for some residual elongation in the finished article. It appears that uni ⁇ axial stretching using the process of the invention gives substantial strength in the transverse direction without the need for much, if any, stretching in the transverse direction.
  • the articles to which the invention is especially applicable are those having relatively thin regions, for example 0.01 to 2, especially 0.1 to 1, mm thick.
  • the process can include co-extrusion or lamination of PHA with a different polymer; the web of such other polymer may be separated from the layer of PHA before the heating step or after the heating step and before step (d), but may be left in position if a duplex article is required and if that polymer has been chosen to withstand the conditions of the heating and stretching steps.
  • the PHA can also be a blend of two or more differing in the value of m.
  • the PHA may be the product of a microbiological process.
  • the microorganism may be wild or mutated or may have had the necessary genetic material introduced into it. Altematively the necessary genetic material may be harboured by a eucaryote, to effect the microbiological process.
  • Microbiologically produced PHA is chiral (R) and stereospecific.
  • FIG. 1 is a schematic representation of the plant in which the production of oriented film may be carried out.
  • Extruder 10 feeds into tubular die 12 fitted with coaxial air supply indicated schematically by 14. Die 12 is disposed in temperature-controlled enclosure 16 and feeds upwards towards the nip of flattening rolls 18 and 20, in open air above enclosure 16.
  • the flattened preform passes around roll 22, then through a slitter/opener (not shown) on to roll 24 held at 70°C, which runs at the same speed as the feed of preform. From roll 24, however, the preform passes over fast roll 26 (also at 70°C) and through the nip of fast rolls 28, 30 and is stretched in the machine direction. If desired a transverse stretch can be effected after rolls 32, 34 by a stenter (not shown). The stretched film is then led out to storage.
  • the PHA was a BV copolymer containing 8 mol % of V and having a molecular weight about 400000.
  • the extruder was a 20 mm laboratory unit feeding a 25 mm diameter circular die 12 in an upward direction.
  • the atmosphere circulated about the extruded preform and through a nozzle in the centre of the die was initially at 25°C, permitting the emerging extrudate to widen to about 50 mm and to crystallise sufficiently in its upward passage to flattening rolls 18, 20 (time about 15 sec) to avoid self-adhesion.
  • the main stretch in rolls 28, 30 was 300-400%.
  • the resulting film was 15-20 ⁇ m thick. Typical properties of the product film were:

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

This invention relates to a process for producing oriented polyhydroxyalkanoate (PHA) that requires less stringent temperature control than previous processes. The process comprises melting the PHA, shaping preform from the melted PHA, stretching the preform a first time in at least one direction, and stretching the preform a second time. In one embodiment, the preform is cooled prior to stretching a second time. In another embodiment, the PHA is laminated with a polymer.

Description

ORIENTED POLYESTER
This invention relates to oriented polyester and in particular to oriented shaped articles made of stereospecific polyhydroxyalkanoate (PHA).
EP-A-0104731 describes a process of making oriented shaped articles, specifically fibre but possibly others such as film, by extruding a preform, effecting a controlled degree of crystallisation, drawing the article and increasing its degree of crystallinity. Such a process, while effective, is difficult to control and inconvenient if it is desired to change line speed.
We have now discovered a procedure in which the need for such careful control is lessened and by which PHA film of attractive properties can be made.
According to the invention a process of producing an oriented PHA article comprises: (a) melting PHA; (b) shaping preform therefrom;
(c) allowing the preform to cool and solidify; and
(d) stretching the preform to cause orientation of the PHA; and is characterised by: between steps (b) and (c) stretching the preform before it has fully solidified. The stretch between steps (b) and (c) will be referred to as "first stretch" and the stretch in step (d) as "second stretch."
The first stretch takes place at a temperature less than the melting point of the PHA typically by 5-20°C, but by not more than 60°C. The temperature profile of the article is controlled to afford the required extent of first stretch. Conveniently this is effected by a current of gas, especially air, at a suitable temperature and flow rate.
The time span of steps (b) and (c) and of first stretch are controlled to bring the preform to a level of crystallinity sufficient to avoid adhesion between PHA layers or between a PHA layer and a guiding surface such as a roller.
The extent of first stretch is incomplete to permit further stretching in step (d) and is, in any event, limited by what is practicable in the incompletely solid condition of the PHA and the fact that it is not accompanied by significant orientation. Typically it is by a factor in the range
2 to 10 in at least one direction. First stretch may be in the machine direction or transverse direction or both. Preferably the preform is a tube and is flattened after solidification; and the first stretch is effected by pressure of fluid, suitably applied coaxially of the extrusion die and contained by the closed end of the tube between flattening rolls. Typical extents of first stretch are in the range 5 to 10 (machine direction) and 2 to 5 (transverse).
The first stretched preform can be passed to step (d) immediately or after a convenient period, which can be up to 10 minutes but possibly longer depending on process conditions.
Step (d) is effected by techniques differing according to the shape of the article being made. For fibre it simply consists in drawing the cast fibre away from a draw point faster than it is being fed to that point; a suitable draw ratio is at least 3, for example in the range 5 to 8. For flat film uni-axial forward stretching is analogous to fibre drawing; instead or, more usually, in addition, transverse stretching is practised, using stenter clamps applied to the sides of the advancing film. For hollow articles such as tubes transverse stretching may be by compressed gas. If desired, tube formed in step (b) may be slit to flat film before step (d) or before heating step for step (d).
The temperature at which step (d) stretching is effected is preferably within 60 to 1 10°C of the PHA melting point.
The degree of stretch in step (d) is preferably in the range 60-80% of the maximum possible, so as to provide for some residual elongation in the finished article. It appears that uni¬ axial stretching using the process of the invention gives substantial strength in the transverse direction without the need for much, if any, stretching in the transverse direction. The articles to which the invention is especially applicable are those having relatively thin regions, for example 0.01 to 2, especially 0.1 to 1, mm thick.
The process can include co-extrusion or lamination of PHA with a different polymer; the web of such other polymer may be separated from the layer of PHA before the heating step or after the heating step and before step (d), but may be left in position if a duplex article is required and if that polymer has been chosen to withstand the conditions of the heating and stretching steps.
Suitable PHAs comprise units of Formula I: -O-CmHn-O- where m is in the range 1-13 and n is 2m or (except when m is unity) 2m-2. Typically CmHn contains 2-5 carbon atoms in the polymer chain and the remainder (if any) in a side chain. In very suitable PHAs m is 3 or 4, n is 2m and especially there are units with m = 3 and m = 4 copolymerised together with respectively a C, and C2 side chain on the carbon next to oxygen. Particular PHAs contain a preponderance of m = 3 units, especially with at least 70 mol % of such units, the balance being units in which m = 4. The molecular weight of the PHA is for example over 50000, especially over 100000, up to eg 2 x 106.
PHA containing only m = 3 units is referred to as PHB; PHA containing m = 3 and m = 4 units is the copolymer PHBV. PHBV preferably contains 4-30 especially 12-25, mol % of m = 4 units. The PHA can also be a blend of two or more differing in the value of m. A particular example contains: (a) PHA consisting essentially of units in which 2-5 mol % of units have m =
4, the rest m = 3; and (b) PHA consisting essentially of Formula I units in which 15-30 mol % of units have m = 4, the rest m = 3. The proportions in such a blend are preferably such as give an average m = 4 content in the range 12-25%. The PHA may be the product of a microbiological process. The microorganism may be wild or mutated or may have had the necessary genetic material introduced into it. Altematively the necessary genetic material may be harboured by a eucaryote, to effect the microbiological process. Microbiologically produced PHA is chiral (R) and stereospecific. Examples of suitable microbiological processes are the following: for Formula I material with m = 3 or m = partly 3, partly 4: EP-A-69497 (Alcaligenes eutrophus): for Formula I materials with m = 3, US4101533 (A. eutrophus ,. EP-A-144017
(A. latus); for Formula I material with m = 7-13, EP-A-0392687 (various Pseudomonas). The microbiological production of the PHA is preferably carried out in two stages: (a) aerobic growth of microorganisms and
(b) aerobic fermentation of the resulting organisms in a medium containing a carbon source but deficient in at least one nutrient essential for growth. The deficient nutrient is preferably phosphate. The PHA is then separated from the PHA-containing cells by a harvesting process in which NPCM is solubilised leaving PHA of high purity, preferably at least 96, especially at least 98%. One preferred form of the process is shown in Figure 1, which is a schematic representation of the plant in which the production of oriented film may be carried out. Extruder 10 feeds into tubular die 12 fitted with coaxial air supply indicated schematically by 14. Die 12 is disposed in temperature-controlled enclosure 16 and feeds upwards towards the nip of flattening rolls 18 and 20, in open air above enclosure 16. From rolls 18, 20 the flattened preform passes around roll 22, then through a slitter/opener (not shown) on to roll 24 held at 70°C, which runs at the same speed as the feed of preform. From roll 24, however, the preform passes over fast roll 26 (also at 70°C) and through the nip of fast rolls 28, 30 and is stretched in the machine direction. If desired a transverse stretch can be effected after rolls 32, 34 by a stenter (not shown). The stretched film is then led out to storage.
In a particular example the PHA was a BV copolymer containing 8 mol % of V and having a molecular weight about 400000. The extruder was a 20 mm laboratory unit feeding a 25 mm diameter circular die 12 in an upward direction. The atmosphere circulated about the extruded preform and through a nozzle in the centre of the die was initially at 25°C, permitting the emerging extrudate to widen to about 50 mm and to crystallise sufficiently in its upward passage to flattening rolls 18, 20 (time about 15 sec) to avoid self-adhesion. The main stretch in rolls 28, 30 was 300-400%. The resulting film was 15-20 μm thick. Typical properties of the product film were:
Machine Direction Transverse Tensile strength MPa 90 80
Elongation to break % 130 150

Claims

WHAT IS CLAIMED IS:
1. A process for producing oriented polyhydroxyalkanoate (PHA), comprising: melting the PHA; shaping preform from the melted PHA for a suitable time; stretching the preform a first time in at least one direction by a suitable factor under suitable conditions of time and temperature; and stretching the preform a second time to a suitable degree at a suitable temperature.
2. The process of Claim 1 further comprising cooling the preform for a suitable time prior to said second stretching.
3. The process of Claim 1 further comprising maintaining the temperature of said first stretching by applying a current of gas under suitable conditions of temperature and flow rate.
4. The process of Claim 3 wherein the gas is air.
5. The process of Claim 1 wherein said first stretching comprises applying a fluid at a suitable pressure.
6. The process of Claim 1 wherein the temperature of said first stretching is 5 °C to 20 °C below the melting point of the PHA.
7. The process of Claim 1 wherein the temperature of said first stretching is not more than 60 °C below the melting point of the PHA.
8. The process of Claim 1 wherein the factor of said first stretching is 2 to 10.
9. The process of Claim 1 wherein the temperature of said second stretching is within 60 °C to 110 °C of the melting point of the PHA.
10. The process of Claim 1 wherein the degree of said second stretching is 60% to 80% of maximum.
11. The process of Claim 1 wherein the PHA is a product of a microbiological process.
12. The process of Claim 1 wherein the PHA consists of repeating units of: - O - CmHn - CO - wherein m is between 1 and 13 and n is 2m or 2m- 1.
13. The process of Claim 1 wherein the PHA is polyhydroxy-butyrate-co-valerate.
14. The process of Claim 1 wherein the preform is a tube.
15. The process of Claim 1 further comprising laminating the PHA with a polymer.
PCT/US1996/020546 1995-12-21 1996-12-18 Oriented polyester WO1997022459A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP9523041A JP2000502298A (en) 1995-12-21 1996-12-18 Oriented polyester
AU13467/97A AU1346797A (en) 1995-12-21 1996-12-18 Oriented polyester
EP96945000A EP0868287A1 (en) 1995-12-21 1996-12-18 Oriented polyester

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9526165.7 1995-12-21
GBGB9526165.7A GB9526165D0 (en) 1995-12-21 1995-12-21 Oriented polyester

Publications (1)

Publication Number Publication Date
WO1997022459A1 true WO1997022459A1 (en) 1997-06-26

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PCT/US1996/020546 WO1997022459A1 (en) 1995-12-21 1996-12-18 Oriented polyester

Country Status (7)

Country Link
EP (1) EP0868287A1 (en)
JP (1) JP2000502298A (en)
AU (1) AU1346797A (en)
CA (1) CA2239898A1 (en)
GB (1) GB9526165D0 (en)
MX (1) MX9805096A (en)
WO (1) WO1997022459A1 (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0849311A2 (en) * 1996-12-18 1998-06-24 THE INSTITUTE OF PHYSICAL & CHEMICAL RESEARCH Poly(3-hydroxybutanoic acid) film
EP0998381A1 (en) 1997-07-25 2000-05-10 The Monsanto Company Polyhydroxyalkanoate coatings
WO2001030893A1 (en) * 1999-10-28 2001-05-03 The Procter & Gamble Company Methods for preparing soft and elastic biodegradable polyhydroxyalkanoate copolymer compositions and polymer products comprising such compositions
WO2001030892A1 (en) * 1999-10-28 2001-05-03 The Procter & Gamble Company Polymer products comprising soft and elastic biodegradable polyhydroxyalkanoate copolymer compositions and methods of preparing such polymer products
WO2003070450A1 (en) * 2002-02-21 2003-08-28 Riken High-strength film of polyhydroxyalkanoic acid and process for producing the same
WO2003091002A1 (en) * 2002-04-25 2003-11-06 Riken High-strength film of polyhydroxyalkanoic acid and process for producing the same
US6794023B1 (en) 1999-10-28 2004-09-21 The Procter & Gamble Company Polymer products comprising soft and elastic biodegradable polyhydroxyalkanoate copolymer compositions and methods of preparing such polymer products
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
WO2005120808A1 (en) * 2004-06-09 2005-12-22 Novamont S.P.A. Process for the production of biodegradable films having improved mechanical properties
GR20050100476A (en) * 2005-09-19 2007-04-25 Πλαστικα Κρητης Αβεε Machine direction oriented mulching film
EP2277681A1 (en) * 2009-07-13 2011-01-26 HOSOKAWA ALPINE Aktiengesellschaft Method and device for regulating the thickness of stretched blow film
WO2024030347A1 (en) * 2022-08-01 2024-02-08 Danimer Ipco, Llc Dimensionally stable biodegradable film

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023189584A1 (en) * 2022-03-29 2023-10-05 株式会社カネカ Method for producing stretched film

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WO1995017454A1 (en) * 1993-12-20 1995-06-29 Monsanto Company Process for preparing films and coatings
US5443780A (en) * 1992-07-09 1995-08-22 Shimadzu Corporation Oriented films of polylactic acid and methods of producing same
US5464689A (en) * 1993-06-15 1995-11-07 Uni-Charm Corporation Resin composition, porous film produced therefrom and process for producing same
EP0736563A1 (en) * 1995-04-07 1996-10-09 SAFTA S.p.A. Process for the manufacture of totally bio-decomposable films with high mechanical characteristics and relevant products and applications

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JPS6169431A (en) * 1984-09-14 1986-04-10 Teijin Ltd Stretching method of poly(beta-hydroxybutyric acid) molded product
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WO1995017454A1 (en) * 1993-12-20 1995-06-29 Monsanto Company Process for preparing films and coatings
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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0849311A2 (en) * 1996-12-18 1998-06-24 THE INSTITUTE OF PHYSICAL & CHEMICAL RESEARCH Poly(3-hydroxybutanoic acid) film
EP0849311A3 (en) * 1996-12-18 1998-12-30 THE INSTITUTE OF PHYSICAL & CHEMICAL RESEARCH Poly(3-hydroxybutanoic acid) film
US5917002A (en) * 1996-12-18 1999-06-29 The Institute Of Physical And Chemical Research Poly(3-hydroxybutanoic acid) film
EP0998381A1 (en) 1997-07-25 2000-05-10 The Monsanto Company Polyhydroxyalkanoate coatings
US6794023B1 (en) 1999-10-28 2004-09-21 The Procter & Gamble Company Polymer products comprising soft and elastic biodegradable polyhydroxyalkanoate copolymer compositions and methods of preparing such polymer products
WO2001030893A1 (en) * 1999-10-28 2001-05-03 The Procter & Gamble Company Methods for preparing soft and elastic biodegradable polyhydroxyalkanoate copolymer compositions and polymer products comprising such compositions
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
WO2001030892A1 (en) * 1999-10-28 2001-05-03 The Procter & Gamble Company Polymer products comprising soft and elastic biodegradable polyhydroxyalkanoate copolymer compositions and methods of preparing such polymer products
WO2003070450A1 (en) * 2002-02-21 2003-08-28 Riken High-strength film of polyhydroxyalkanoic acid and process for producing the same
WO2003091002A1 (en) * 2002-04-25 2003-11-06 Riken High-strength film of polyhydroxyalkanoic acid and process for producing the same
EP1755864B2 (en) † 2004-06-09 2014-08-13 NOVAMONT S.p.A. Process for the production of biodegradable films having improved mechanical properties
WO2005120808A1 (en) * 2004-06-09 2005-12-22 Novamont S.P.A. Process for the production of biodegradable films having improved mechanical properties
NO338782B1 (en) * 2004-06-09 2016-10-17 Novamont Spa Process for the preparation of biodegradable films having improved mechanical properties
GR20050100476A (en) * 2005-09-19 2007-04-25 Πλαστικα Κρητης Αβεε Machine direction oriented mulching film
US9302423B2 (en) 2009-07-13 2016-04-05 Hosakawa Alpine Aktiengesellschaft Process to regulate the thickness of oriented blown film
EP2277681A1 (en) * 2009-07-13 2011-01-26 HOSOKAWA ALPINE Aktiengesellschaft Method and device for regulating the thickness of stretched blow film
WO2024030347A1 (en) * 2022-08-01 2024-02-08 Danimer Ipco, Llc Dimensionally stable biodegradable film
WO2024030834A1 (en) * 2022-08-01 2024-02-08 Danimer Ipco, Llc Biaxially-oriented biodegradable film

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CA2239898A1 (en) 1997-06-26
JP2000502298A (en) 2000-02-29
EP0868287A1 (en) 1998-10-07
AU1346797A (en) 1997-07-14
MX9805096A (en) 1998-10-31
GB9526165D0 (en) 1996-02-21

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