WO2007060184A2 - Biodegradable hollow strips - Google Patents

Biodegradable hollow strips Download PDF

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Publication number
WO2007060184A2
WO2007060184A2 PCT/EP2006/068777 EP2006068777W WO2007060184A2 WO 2007060184 A2 WO2007060184 A2 WO 2007060184A2 EP 2006068777 W EP2006068777 W EP 2006068777W WO 2007060184 A2 WO2007060184 A2 WO 2007060184A2
Authority
WO
WIPO (PCT)
Prior art keywords
flexible hollow
strip according
hollow strip
aliphatic
aromatic
Prior art date
Application number
PCT/EP2006/068777
Other languages
French (fr)
Other versions
WO2007060184A3 (en
Inventor
Roberto Marangon
Original Assignee
Novamont S.P.A.
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 Novamont S.P.A. filed Critical Novamont S.P.A.
Publication of WO2007060184A2 publication Critical patent/WO2007060184A2/en
Publication of WO2007060184A3 publication Critical patent/WO2007060184A3/en

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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
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • 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
    • 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
    • C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
    • 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
    • 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
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B29K2067/046—PLA, i.e. polylactic acid or polylactide
    • 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
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0059—Degradable
    • B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible

Definitions

  • the present invention relates to flexible hollow strips produced with biodegradable materials, such as aliphatic-aromatic polyesters. Said strips have mechanical properties that are the same as or superior to those of a hollow strip made of PVC, and properties of use that are acceptable also under UV ageing. Moreover, they are extrudable with the same machines used for hollow strips made of PVC.
  • Hollow strips made of PVC are used in many applications in which. These range from the agricultural field, such as systems for binding plants or irrigation pipes, to the medical field, such as tubes for catheters or for infusion or for use as haemostats, or as sheaths for wires or the like. In most cases hollow flexible strips are products used for a limited time, and there is a risk that they are abandoned in the environment, as it occurs in the case of strings for agricultural use.
  • a flexible hollow strip characterized in that it is made substantially of a biodegradable material comprising an aliphatic-aromatic biodegradable polyester obtained from a dicarboxylic acid and a diol.
  • a further advantage of the hollow strip according to the invention is represented by the possibility of obtaining products that are lighter than PVC, which can be manufactured at a cost substantially similar to those of tubes made of conventional material.
  • the flexible hollow strips according to the invention comprise aliphatic-aromatic biodegradable polyesters obtainable from a dicarboxylic acid and a diol.
  • Particularly suitable according to the invention are polyesters with an elastic modulus of between 40 and 500, preferably between 45 and 350 and more preferably between 50 and 250 MPa, measured on dumbbell according to the standard ASTM D-638, and a melt flow index (MFI) (temp., load) of between 0.5 and 50, preferably between 1 and 25 g/10 min, more preferably between 2 and 20 g/10 min and even more preferably between 3 and 15 g/10 min.
  • MFI melt flow index
  • Particularly preferred are hollow strips obtained from aliphatic-aromatic biodegradable polyesters with a high content of aromatic carboxylic acid, or its derivatives.
  • aliphatic- aromatic biodegradable polyesters with a content of aromatic dicarboxylic acid (calculated with respect to the total moles of acid) greater than 46 mol%, in particular comprised between 49 and 70 mol%, preferably between 50 and 65 mol%, and even more preferably between 50 and
  • Said polymers can contain in the main chain co-monomers of the hydroxyacid type, such as for example lactic acid or its lactides, glycolic acid or its glycolides, caprolactone or hydroxycaproic acid.
  • polyesters containing aliphatic diacids such as sebacic acids, azelaic acid and brassylic acid, and their mixtures.
  • Said polyesters are able to maintain a good rate of biodegradation also with a high content of aromatic acid, and are more easily extrudable, thanks to the faster rate of crystallization of the polyester during extrusion.
  • polyesters of the aliphatic-aromatic type used to make the flexible hollow strips according to the invention can be mixed with other polymers and/or with other substances, such as natural or synthetic fillers, stabilizing agents, colouring agents, and additives of various nature.
  • polymers suitable to be mixed with the above cited polyesters are: polymers of natural origin such as polysaccharides, aliphatic-aromatic polyesters, aliphatic polyesters such as polyalkylene -sebacates, -azelates, -brassylates and their copolymers, polybutylene succinates adipates, lactates, PLA (polylactic acid) and PHB (polyhydroxy butyrrate) polymers and copolymers, and polycaprolactones.
  • polymers of natural origin such as polysaccharides, aliphatic-aromatic polyesters, aliphatic polyesters such as polyalkylene -sebacates, -azelates, -brassylates and their copolymers, polybutylene succinates adipates, lactates, PLA (polylactic acid) and PHB (polyhydroxy butyrrate) polymers and copolymers, and polycaprolactones.
  • biodegradability it is meant the biodegradability measured according to the standard EN 13432.
  • the product shows a high resistance to UV ageing.
  • the mechanical performance of the strings according to the invention can be improved.
  • the green pigments added to the aliphatic-aromatic polyester enable a lengthening of the service life of the strip once this is exposed to UV rays.
  • the flexible hollow strips according to the invention can also be stretched. Stretching enables to obtain a product characterized by a good elasticity, eliminating the excessive lengthening in the plastic-deformation region typical of this family of polymers. Ideal stretching ratios are between 1:1.5 and 1:5, preferably between 1:1.7 and 1:3.5, more preferably between 1:2 and
  • the hollow sectional strips according to the invention can also be weaved in order to create complex shapes.
  • MFR melt flow rate
  • Pantone color Clariant 3435/C was added, while for examples 3 and 5 a Schulman masterbatch of the GREEN 3315 type was added.
  • the extruder was equipped with a double threading die, with a system for blowing in air for inflating and calibrating the extruded tube. The processability proved comparable to that of a traditional PVC.
  • the process of stretching was performed with a stretching ratio ranging between 1:2 and 1:5 .
  • Strips 2, 3 and 4 are referred to as thin-walled strips, whereas the strips 4 and 5 are referred to as thick- walled strips.
  • Relative humidity 62%; resting-surface temperature: 60 0 C; ambient temperature: 32°C

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Flexible hollow strip made of a biodegradable material comprising an aliphatic-aromatic biodegradable polyester obtainable from a dicarboxylic acid and a diol, whrein the aliphatic- aromatic biodegradable polyester has an elastic modulus comprised between 40 and 500 MPa measured on dumbbell according to the standard ASTM D-638.

Description

BIODEGRADABLE HOLLOW STRIPS
DESCRIPTION
The present invention relates to flexible hollow strips produced with biodegradable materials, such as aliphatic-aromatic polyesters. Said strips have mechanical properties that are the same as or superior to those of a hollow strip made of PVC, and properties of use that are acceptable also under UV ageing. Moreover, they are extrudable with the same machines used for hollow strips made of PVC.
Hollow strips made of PVC are used in many applications in which. These range from the agricultural field, such as systems for binding plants or irrigation pipes, to the medical field, such as tubes for catheters or for infusion or for use as haemostats, or as sheaths for wires or the like. In most cases hollow flexible strips are products used for a limited time, and there is a risk that they are abandoned in the environment, as it occurs in the case of strings for agricultural use.
Therefore, it is an object of the present invention to disclose a new product having characteristics similar to the products available on the market, such as PVC, but having additionally the characteristic of being readily biodegradable in the environment. The above and other objects and advantages of the invention are achieved by a flexible hollow strip characterized in that it is made substantially of a biodegradable material comprising an aliphatic-aromatic biodegradable polyester obtained from a dicarboxylic acid and a diol. A further advantage of the hollow strip according to the invention is represented by the possibility of obtaining products that are lighter than PVC, which can be manufactured at a cost substantially similar to those of tubes made of conventional material. The flexible hollow strips according to the invention comprise aliphatic-aromatic biodegradable polyesters obtainable from a dicarboxylic acid and a diol. Particularly suitable according to the invention are polyesters with an elastic modulus of between 40 and 500, preferably between 45 and 350 and more preferably between 50 and 250 MPa, measured on dumbbell according to the standard ASTM D-638, and a melt flow index (MFI) (temp., load) of between 0.5 and 50, preferably between 1 and 25 g/10 min, more preferably between 2 and 20 g/10 min and even more preferably between 3 and 15 g/10 min. Particularly preferred are hollow strips obtained from aliphatic-aromatic biodegradable polyesters with a high content of aromatic carboxylic acid, or its derivatives. In particular, especially advantageous are aliphatic- aromatic biodegradable polyesters with a content of aromatic dicarboxylic acid (calculated with respect to the total moles of acid) greater than 46 mol%, in particular comprised between 49 and 70 mol%, preferably between 50 and 65 mol%, and even more preferably between 50 and
60 mol%.
Said polymers can contain in the main chain co-monomers of the hydroxyacid type, such as for example lactic acid or its lactides, glycolic acid or its glycolides, caprolactone or hydroxycaproic acid.
Particularly preferred are aliphatic-aromatic polyesters containing aliphatic diacids, such as sebacic acids, azelaic acid and brassylic acid, and their mixtures. Said polyesters are able to maintain a good rate of biodegradation also with a high content of aromatic acid, and are more easily extrudable, thanks to the faster rate of crystallization of the polyester during extrusion.
The polyesters of the aliphatic-aromatic type used to make the flexible hollow strips according to the invention can be mixed with other polymers and/or with other substances, such as natural or synthetic fillers, stabilizing agents, colouring agents, and additives of various nature.
Examples of polymers suitable to be mixed with the above cited polyesters are: polymers of natural origin such as polysaccharides, aliphatic-aromatic polyesters, aliphatic polyesters such as polyalkylene -sebacates, -azelates, -brassylates and their copolymers, polybutylene succinates adipates, lactates, PLA (polylactic acid) and PHB (polyhydroxy butyrrate) polymers and copolymers, and polycaprolactones.
In the present description, with "biodegradability" it is meant the biodegradability measured according to the standard EN 13432.
In a particular embodiment of the invention, the product shows a high resistance to UV ageing.
It has in fact been found that by pigmenting the strip with pigments of different colours, such as black, brown or green, that are able to absorb selectively the light in the UV and visible wavelength, the mechanical performance of the strings according to the invention can be improved. In particular, the green pigments added to the aliphatic-aromatic polyester enable a lengthening of the service life of the strip once this is exposed to UV rays.
The flexible hollow strips according to the invention can also be stretched. Stretching enables to obtain a product characterized by a good elasticity, eliminating the excessive lengthening in the plastic-deformation region typical of this family of polymers. Ideal stretching ratios are between 1:1.5 and 1:5, preferably between 1:1.7 and 1:3.5, more preferably between 1:2 and
1:3.
For particular applications it is possible to have stretching ratios higher than those cited above.
The hollow sectional strips according to the invention can also be weaved in order to create complex shapes. EXAMPLES
Material
Polybutylene sebacate co-terephthalate containing 54% of terephthalic acid with respect to the total units of acid with melt flow rate (MFR) of 10.3 g/10 min and a modulus of 90 MPa.
In Examples 2-5, 2% of a green masterbatch was added. In particular for examples 2 and 4 the
Pantone color Clariant 3435/C was added, while for examples 3 and 5 a Schulman masterbatch of the GREEN 3315 type was added.
Extrusion and stretching process
A single-screw extruder for PVC was used, with a diameter of 45 mm, L/D = 30, and with a thermal profile in the 130-1600C range along the screw up to the head. Screw r.p.m. adjusted between 10 and 20 r.p.m. The extruder was equipped with a double threading die, with a system for blowing in air for inflating and calibrating the extruded tube. The processability proved comparable to that of a traditional PVC.
The process of stretching was performed with a stretching ratio ranging between 1:2 and 1:5 .
The hollow strip obtained immediately after extrusion in the absence of stretching did not yet present a behaviour similar to that of PVC.
Strips 2, 3 and 4 are referred to as thin-walled strips, whereas the strips 4 and 5 are referred to as thick- walled strips.
Figure imgf000004_0001
Mechanical characterization of the specimens The table below shows the results of the tensile tests conducted on the specimens gathered.
Figure imgf000005_0001
The tensile tests were conducted both at 50 mm/min and at 1000 mm/min. This enabled the behaviour of the product at a low rate of deformation (namely, in conditions that simulate the growth of a plant) to be known, but also at a high rate of deformation (namely, in conditions that simulate the operation of binding the strip to the shoot of a plant). In the case of a string for agricultural uses, in fact, this is wound around the shoot of the plant and around the support on which the shoot itself is to be fastened so as to enable the operator to make a knot, after which the strip is not cut but broken away from a clew by the operator himself. Whereas in the case of PVC the effect of the test rate is reasonably negligible, in the case of the strip obtained with aliphatic-aromatic polyester there is noted a drop in the ultimate strength as the tensile rate increases. This phenomenon is favourable for the application, since it allows the operator to find less resistance when he breaks the strip during the operations of binding (i.e., he subjects the sectional strip to a tensile stress at a high rate).
If the product is sized according to the criterion of having mechanical characteristics similar to those of PVC, it is evident that the material of the invention permits to obtain a strip that is much lighter than a conventional strip having the same strength, with a consequent significant reduction of costs. UV-ageing test
Conditions of irradiation for ageing test:
Global radiation (w/m2): 384, UVA radiation (w/m2): 13, UVB radiation (w/m2): 1
Relative humidity: 62%; resting-surface temperature: 600C; ambient temperature: 32°C
Figure imgf000006_0001

Claims

1. Flexible hollow strip, characterized in that it is substantially made of a biodegradable material comprising an aliphatic-aromatic biodegradable polyester obtainable from a dicarboxylic acid and a diol.
2. Flexible hollow strip according to Claim 1, characterized in that said aliphatic-aromatic biodegradable polyester has an elastic modulus comprised between 40 and 500 MPa measured on dumbbell according to the standard ASTM D-638.
3. Flexible hollow strip according to Claim 1, characterized in that said aliphatic-aromatic biodegradable polyester has an elastic modulus comprised between 45 and 350 MPa measured on dumbbell according to the standard ASTM D-638.
4. Flexible hollow strip according to Claim 1, characterized in that said aliphatic-aromatic biodegradable polyester has an elastic modulus comprised between 50 and 250 MPa, measured on dumbbell according to the standard ASTM D-638.
5. Flexible hollow strip according to Claim 1, characterized in that said aliphatic-aromatic biodegradable polyester has a MFI comprised between 0.5 and 50.
6. Flexible hollow strip according to Claim 1, characterized in that said aliphatic-aromatic biodegradable polyester has A MFI comprised between 1 and 25 g/10 min.
7. Flexible hollow strip according to Claim 1, characterized in that said aliphatic-aromatic biodegradable polyester has a MFI comprised between 2 and 20 g/10 min.
8. Flexible hollow strip according to Claim 1, characterized in that said aliphatic-aromatic biodegradable polyester has a MFI comprised between 3 and 15 g/10 min.
9. Flexible hollow strip according to Claim 2, characterized in that said aliphatic-aromatic biodegradable polyester has a content of aromatic dicarboxylic acid greater than 46 mol%.
10. Flexible hollow strip according to Claim 9, characterized in that said aliphatic-aromatic biodegradable polyester has a content of aromatic dicarboxylic acid comprised between 49 and 70 mol%.
11. Flexible hollow strip according to Claim 9, characterized in that said aliphatic-aromatic biodegradable polyester has a content of aromatic dicarboxylic acid comprised between 50 and 65 mol%.
12. Flexible hollow strip according to Claim 9, characterized in that said aliphatic-aromatic biodegradable polyester has a content of aromatic dicarboxylic acid comprised between 50 and 60 mol%.
13. Flexible hollow strip according to Claim 9, characterized in that said aliphatic-aromatic biodegradable polyester contains units derived from a hydroxyacid.
14. Flexible hollow strip according to Claim 9, characterized in that said aliphatic dicarboxylic acid is selected from the group consisting of sebacic acids, azelaic acid, brassylic acid and their mixtures.
15. Flexible hollow strip according to Claim 1, characterized in that said biodegradable material comprises products other than said aliphatic-aromatic biodegradable polyesters.
16. Flexible hollow strip according to Claim 14, characterized in that said products are polymers of natural origin..
17. Flexible hollow strip according to Claim 15, characterized in that said polymers of natural origin are selected from the group consisting of polysaccharides, aliphatic polyesters including polyalkylene sebacates, azelates, brassylates and their copolymers, polybutylene succinates adipates, lactates, polylactic acid and polyhydroxy butyrrate polymers and copolymers, and polycaprolactones.
18. Flexible hollow strip according to Claim 14, characterized in that said products are selected from the group consisting of natural or synthetic fillers, stabilizing agents, colouring agents, and additives.
19. Flexible hollow strip according to Claim 14, characterized by comprising a black, brown or green pigment, able to absorb selectively the light in the UV and visible wavelength.
20. Flexible hollow strip according to any one of the preceding claims, characterized by being stretched at a stretching ratio comprised between 1:1.5 and 1:5.
21. Flexible hollow strip according to Claim 19, characterized by a stretching ratio comprised between 1 : 1.7.
22. Flexible hollow strip according to Claim 19, characterized by a stretching ratio comprised between 1:3.5.
23. Flexible hollow strip according to Claim 19, characterized by a stretching ratio comprised between 1:2 and 1:3.
24. Flexible hollow strip according to any one of the preceding claims for use as string for agricultural uses.
25. Flexible hollow sectional strip according to any one of the preceding claims for use as string to create complex shapes.
PCT/EP2006/068777 2005-11-24 2006-11-22 Biodegradable hollow strips WO2007060184A2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI2005A002244 2005-11-24
ITMI20052244 ITMI20052244A1 (en) 2005-11-24 2005-11-24 BIODEGRADABLE CABLES PROFILES

Publications (2)

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WO2007060184A2 true WO2007060184A2 (en) 2007-05-31
WO2007060184A3 WO2007060184A3 (en) 2007-08-09

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2536582A1 (en) * 2013-11-25 2015-05-26 Plàstics Torner, S.L. Plastic tie, use of tie and method to tie, gather or join elements together (Machine-translation by Google Translate, not legally binding)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1533875A (en) * 1976-05-10 1978-11-29 Rapidex Prod Ltd Tree-tie cushions and tree-ties
DE2822039A1 (en) * 1978-05-20 1979-11-29 Pollmeier Gmbh Binding for tying up plants - consists of weather resistant flat elastic strip with adhesive coating on one side
FR2853330A1 (en) * 2003-04-01 2004-10-08 Univ Bretagne Sud METHOD AND DEVICE FOR MANUFACTURING BIODEGRADABLE THREADS OR TWINS, THREADS OR TWINS OBTAINED BY THIS METHOD AND APPLICATIONS THEREOF
US20040225269A1 (en) * 2003-05-08 2004-11-11 The Procter & Gamble Company Molded or extruded articles comprising polyhydroxyalkanoate copolymer and an environmentally degradable thermoplastic polymer
US20050137303A1 (en) * 2003-12-19 2005-06-23 Shelby Marcus D. Blends of aliphatic-aromatic copolyesters with ethylene-vinyl acetate copolymers
US20050171250A1 (en) * 2004-01-30 2005-08-04 Hayes Richard A. Aliphatic-aromatic polyesters, and articles made therefrom

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1533875A (en) * 1976-05-10 1978-11-29 Rapidex Prod Ltd Tree-tie cushions and tree-ties
DE2822039A1 (en) * 1978-05-20 1979-11-29 Pollmeier Gmbh Binding for tying up plants - consists of weather resistant flat elastic strip with adhesive coating on one side
FR2853330A1 (en) * 2003-04-01 2004-10-08 Univ Bretagne Sud METHOD AND DEVICE FOR MANUFACTURING BIODEGRADABLE THREADS OR TWINS, THREADS OR TWINS OBTAINED BY THIS METHOD AND APPLICATIONS THEREOF
US20040225269A1 (en) * 2003-05-08 2004-11-11 The Procter & Gamble Company Molded or extruded articles comprising polyhydroxyalkanoate copolymer and an environmentally degradable thermoplastic polymer
US20050137303A1 (en) * 2003-12-19 2005-06-23 Shelby Marcus D. Blends of aliphatic-aromatic copolyesters with ethylene-vinyl acetate copolymers
US20050171250A1 (en) * 2004-01-30 2005-08-04 Hayes Richard A. Aliphatic-aromatic polyesters, and articles made therefrom

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2536582A1 (en) * 2013-11-25 2015-05-26 Plàstics Torner, S.L. Plastic tie, use of tie and method to tie, gather or join elements together (Machine-translation by Google Translate, not legally binding)

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WO2007060184A3 (en) 2007-08-09

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