WO2006003280A1 - Composition thermoplastique biodegradable et procede de preparation - Google Patents
Composition thermoplastique biodegradable et procede de preparation Download PDFInfo
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- WO2006003280A1 WO2006003280A1 PCT/FR2005/001363 FR2005001363W WO2006003280A1 WO 2006003280 A1 WO2006003280 A1 WO 2006003280A1 FR 2005001363 W FR2005001363 W FR 2005001363W WO 2006003280 A1 WO2006003280 A1 WO 2006003280A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
Definitions
- the present invention relates to biodegradable thermoplastic polymer compositions.
- Thermoplastic polymers are used increasingly important because of their low cost, their stability, their resistance to water, oils, their resistance to degradation such as corrosion or putrefaction and their moldability.
- polyesters of the PET family polyethylene glycol terephthalate and derivatives
- PBT polybutylene glycol terephthalate and derivatives
- PET polyethylene glycol terephthalate and derivatives
- PBT polybutylene glycol terephthalate and derivatives
- these polymers then become considerably more vulnerable. They can hydrolyze spontaneously in a humid environment or through the action of enzymes produced by microbes or microorganisms in the soil, the environment or in composters.
- polyethylene, polypropylene, polystyrene are difficult to degrade under the usual conditions.
- very fine fibers from a few nanometers to a micron are more fragile.
- the degradability of a polymer is therefore a relative notion. It can be modulated.
- some plastics or similar products are biodegradable.
- cellophane which is a particular physical state of the cellulose, certain cellulose derivatives, in particular cellulose diacetate, carboxymethyl cellulose or hydroxyethyl cellulose (condensation product of cellulose with ethylene oxide), poly-glycolic acid (PGA), poly -lactic (PLA), poly-hydroxy-butyric (PHB) or poly-hydroxy-valeric acid (PHV).
- PGA poly-glycolic acid
- PDA poly -lactic
- PHB poly-hydroxy-butyric
- PV poly-hydroxy-valeric acid
- the object of the present invention is to develop a family of biodegradable thermoplastic polymers capable of replacing polyethylene, polypropylene, polystyrene, at least in some of their applications, that is to say, keeping the physical properties of the compositions thermoplastics, the compositions selected to be implemented by the current techniques of the profession without requiring the use of specific equipment.
- US-A-4 156 666 relates to the modification of polyethylene (PE), mixed polymers ethylene / propylene or mixtures of PE and polypropylene (PP) by additives such as unsaturated fatty acids or their esters and possibly a calcium-based filler such as calcium carbonate (limestone), calcium sulphate (plaster or gypsum), calcium phosphate, or a magnesium-based filler : carbonate, silicate.
- PES polyethylene
- PP polypropylene
- additives such as unsaturated fatty acids or their esters and possibly a calcium-based filler such as calcium carbonate (limestone), calcium sulphate (plaster or gypsum), calcium phosphate, or a magnesium-based filler : carbonate, silicate.
- a calcium-based filler such as calcium carbonate (limestone), calcium sulphate (plaster or gypsum), calcium phosphate, or a magnesium-based filler : carbonate, silicate.
- US-A-4,931,488 discloses the use of a biodegradable additive of the family of starch (high molecular weight organic molecule), optionally chemically modified.
- the other additives used in the composition are an iron salt of a fatty acid such as ferrous stearate and an unsaturated fatty acid, therefore easily oxidizable, or an ester thereof.
- starch, its derivatives, as well as cellulose have a poor resistance to heat. They begin to decompose at temperatures barely above 100 ° C, yellowing in a first stage and then charring which can give black spots in the material, and giving off water vapor, which will give bubbles in the final product.
- the international patent application WO-A-94/13735 is similar to the previous application.
- the proposed solution is to formulate a stable polymer with a biodegradable component and other additives, so as to constitute a biodegradable synthetic polymer.
- the biodegradable compounds are preferably selected from the family of polysaccharides of which starch and cellulose are part, plus an oxidizable fatty acid or its ester and iron salts and copper salts.
- compositions therefore meet the problems indicated above, that is to say a moderate heat resistance and / or an abrasive effect on the processing equipment.
- the present invention therefore relates to a biodegradable thermoplastic polyester composition not comprising metals, metal salts or starch and comprising:
- thermoplastic polyester A) at least 50% by weight of a thermoplastic polyester
- thermoplastic polymer other than component A from 2% to 20% by weight of a low molecular weight biodegradable organic molecule, C) from 0 to 30% by weight of a thermoplastic polymer other than component A.
- thermoplastic polyester composition means any polymeric composition based on one or more thermoplastic polyester (s) (component A), which may contain up to 30% of a thermoplastic polymer. different from component A (component C) and from 2 to 20% of a biodegradable organic molecule of low molecular weight (component B).
- component A is chosen from polyethylene glycol terephthalate, polypropylene glycol terephthalate, polybutylene glycol terephthalate and poly 1,3 propanediol terephthalate, polyethylene naphthalate, poly omega caprolactone or mixtures thereof.
- component A has a Tg (glass transition temperature) greater than 40 ° C.
- the component C is a polymer selected from the group consisting of polyurethane (PU), polyester, polystyrene (PS) and polyolefins such as polyethylene (PE), polypropylene (PP) and their copolymers, these polymers including low density polyethylenes (PELDs), high density polyethylenes (HDPE), medium density polyethylenes (MDPEs), linear low density polyethylenes (PELDLs) or their blends.
- PELDs low density polyethylenes
- HDPE high density polyethylenes
- MDPEs medium density polyethylenes
- PELDLs linear low density polyethylenes
- this component C may also be chosen from the group of thermoplastic copolymers or their mixtures such as copolymers of ethylene and vinyl acetate (EVA), in particular Evatane® sold by the company Atofina, copolymers of ethylene and of methyl acrylate (EMAC) such as Orevac® marketed by Atofina, butylene butylacrylate (EBAC), polymethylacrylate (PMA), polymethylmethacrylate (PMMA) and polyethylene oxide or polyethylene glycol (PEG) or mixtures thereof.
- EVA ethylene and vinyl acetate
- EBAC methyl acrylate
- PMA polymethylacrylate
- PMMA polymethylmethacrylate
- PEG polyethylene oxide or polyethylene glycol
- Component C may also be a thermoplastic polyester other than component A and selected from the group consisting of polyethylene naphthalate, polyethylene glycol terephthalate, polypropylene glycol terephthalate, polybutylene glycol terephthalate, poly 1,3 propanediol terephthalate or poly omega caprolactone their mixtures.
- the component C is chosen from the group consisting of copolymers of ethylene and of vinyl acetate or of methyl acrylate or polyethylene naphthalate.
- the component C is a mixture of thermoplastic polymers.
- the composition according to the present invention does not contain starch.
- starch means any starch that is natural, esterified or modified in another way, for example by means of silane.
- the composition according to the present invention contains no polymer other than thermoplastic polymers.
- polymers selected from the group consisting of cellulose and its derivatives, starch derivatives, alginates, chitin, chitosan and polysaccharides in general.
- composition according to the present invention does not contain proteins.
- composition according to the present invention does not include metals or metal salts.
- composition according to the present invention does not comprise abrasive substances.
- abrasive substances any substance that may cause premature wear of the material such as the metal salts defined above.
- the group of "naturally biodegradable" polyesters is not useful in the present invention, although they may be added, such as polyglycolic acid (PGA), poly-lactic acid (PLA), polyhydroxy Butyric acid (PHB), polyhydroxy valeric acid (PHV), ethylene glycol poly-succinate or butylene glycol poly-succinate.
- PGA polyglycolic acid
- PLA poly-lactic acid
- PHB polyhydroxy Butyric acid
- PV polyhydroxy valeric acid
- ethylene glycol poly-succinate or butylene glycol poly-succinate.
- the composition will therefore contain none of these polyesters.
- biodegradable thermoplastic polyester composition means any thermoplastic polyester composition as defined above which disintegrates into small particles either under the action of the heat in a humid atmosphere and / or the conditions of the invention. composting. Since the thermoplastic composition also contains a naturally biodegradable substance, the small particles thus formed are further degraded by microorganisms such as bacteria, yeasts, fungi and / or enzymes present in them. composting mixtures or in the soil. Complete degradation is thus obtained under adequate conditions.
- biodegradable organic molecule means any organic molecule that can degrade under the conditions indicated above for the biodegradable thermoplastic polyester composition.
- the term "low molecular weight organic molecule” is understood to mean any molecule having a molecular weight of less than 5000, advantageously less than 2000.
- the biodegradable organic molecule (component B) is chosen from group consisting of ethylene glycol diacetate (EGDA); glycerol triacetate and polyol esters diethylene glycol diacetate (DEGDA); triethylene glycol diacetate (TEGDA); polyethylene glycol diacetate (PEGDA) and analogous esters derived from propylene oxide; monoesters or diesters of short chain acids and alcohols, chosen in particular from ethylene glycol or propylene glycol di stearate, methyl stearate, glycerol tristearate or ethyl butyl adipate or methyl; monoesters or diesters of short-chain acid and fatty alcohol, in particular chosen from dodecyl acetate, n-octyl succinate or do
- component B is chosen from fatty esters, triethylene glycol diacetate, dodecyl acetate or ethylene glycol di stearate. Even more advantageously, it is triethylene glycol diacetate.
- the amounts of component B used are advantageously between 2 and 10% by weight, even more advantageously between 3 and 6% by weight, and even more advantageously between 4 and 5% by weight. Even more advantageously, it is 5% by weight.
- the composition according to the present invention has good heat stability, preferably at a temperature between room temperature and 300 ° C. At a temperature of 300 ° C., the composition according to the present invention is in the liquid state.
- the term "ambient temperature” means a temperature of approximately 20 ° C.
- good heat stability means the absence of color change, in particular yellowing or blackening, or carbonization of the composition according to the present invention.
- composition according to the present invention may comprise other ingredients, such as, for example, plasticizers, pigments or dyes, antistats, flame retardants, lubricants, nucleating agents, internal lubricants, release agents or anti-wrinkle agents. .
- the composition according to the present invention retains properties comparable to those of thermoplastic compositions, that is to say, for example, a simple implementation and interesting mechanical properties.
- the composition according to the present invention remains stable during storage and intended uses but can be easily degraded after use under the conditions indicated above.
- the composition according to the present invention can be degraded in less than 3 months, advantageously between 1 and 2 months, in an artificial compost.
- the artificial compost is produced in 500 ml flasks containing 50 g of microcrystalline cellulose (Alfa Aesar Avocado) suspended in 150 ml of an IM phosphate buffer, pH 8.0, supplemented with 1 ml of a cocktail of vitamins ("Alvityl syrop", Laboratoires Solvay Pharma), 2 g of sucrose and 1 ml of a cocktail of trace elements ("Aguettant trace elements", Laboratoires Aguettant), 2 g of a cocktail of amino acids (pancreatic casein hydrolyzate, Fluka), 2 g of peanut oil and inoculated with a cocktail of soil microorganisms.
- compositions according to the present invention are stable at temperatures below 0 ° C.
- the degradation tests are carried out as follows: the flasks contain the artificial compost and samples of the test composition: a sheet of 10x15 cm per flask (ie about 1.25 g). They are stirred mechanically, kept in an atmosphere saturated with water and maintained at the chosen temperature. It is estimated that the product is degraded when at least 90% of its weight has disappeared. The tests were always carried out on film-like samples with a thickness of 50 microns +/- 10 microns of compositions according to the present invention.
- the present invention also relates to articles comprising a composition according to the present invention, in particular, made from a composition according to the present invention.
- a composition according to the present invention is a thin film, that is to say of thickness between 10 and 100 microns, of a thick film, that is to say of thickness between 100 microns and 1 mm, a thermoformable film, an injected article, molded or expanded.
- the present invention relates to a process for the preparation of a composition according to the present invention by mixing component A with component B and optionally component C at the processing temperature of the most viscous polymer among components A and C .
- the mixture of polymers (solids at ambient temperature) and low molecular weight additives (usually liquid) is generally produced in an extruder, advantageously of the twin-screw type, advantageously at a temperature of approximately 210 ° C.
- an extruder advantageously of the twin-screw type, advantageously at a temperature of approximately 210 ° C.
- a ring is obtained which is cooled with water and cut into granules. These granules are carefully dried before further use.
- Thin films, 10 to 100 microns, are generally obtained by the extrusion blow molding technique.
- An annular die extrudes a tube that is inflated with air to obtain the desired thickness.
- Thick films, of the order of mm are generally obtained by calendering.
- Example 1 Preparation of PETG granules containing a liquid additive: TEGDA.
- the PETG of the study is the PETG reference 6763 marketed by Eastman Chemicals. This product is a copolymer of terephthalic acid and ethylene glycol supplemented with cyclohexyl 1,4-dimethanol. This product is not considered biodegradable.
- the PETG is dried at least 4 hours at 70 ° C before any intervention.
- the mixture of PETG and TEGDA (triethylene glycol diacetate) is made using a twin-screw extruder brand CLEXTRAL BC21 which has two feed hoppers.
- TEGDA liquid at room temperature
- the speed of rotation of the screws is 300 revolutions per minute and the temperatures close to 220 ° C.
- a rod of about 3 mm in diameter is obtained, which is cooled with water and cut into granules of 3 mm long approx. These granules are thoroughly dried for at least 24 hours at 45 ° C before further use.
- TEGDA amount of TEGDA incorporated was 2; 3; 5; 6; 7.5 and 10% by weight of the final preparation.
- the granules with 10% TEGDA are slightly sticky, which is not the case for the lower dosages.
- Example 2 Preparation of PETG granules containing other liquid additives.
- Example 3 Preparation of thin films PETG / TEGDA.
- Thin films 10 to 100 microns, are obtained by the extrusion blow molding technique.
- a COLLIN brand blowing tool is used which is adapted to a MAPRE single-screw extruder, having a screw 30 mm in diameter and 33 D in length (ie one meter).
- Eight temperature zones can be controlled: three from the hopper, one on the degassing zone, three at the end of the screw and one at the level of the die.
- the following temperature profile was used (° C): 190 (hopper), 190, 180, 170 ( degassing), 180, 200, 200, 220 (die). The rotational speed of the screw is 35 rpm.
- the ring die with a diameter of 50 mm extrudes a 1 mm thick tube which is inflated with compressed air and simultaneously stretched to obtain the desired thickness, most often 50 microns +/- 10 ⁇ m.
- the temperature of the extruder is lower: 140 to 160 ° C.
- PETG supplemented with triethylene glycol diacetate (TEGDA) becomes biodegradable.
- TEGDA partially soluble in water and able to migrate into the PETG matrix, is degraded first to leave the PETG in a microporous and hydrophilic form that becomes accessible to degradation by microorganisms in the soil or the soil. environment. It will be noted that such a formulation may not be suitable for the long-term conditioning of wet products, except for the packaging of products to be kept at low temperature (freezer, refrigerator).
- T g glass transition temperature
- the ideal proportion of TEGDA is between 3 and 6%, by weight.
- the degradation times vary from 1 month (6% of TEGDA) to two months (3% of TEGDA) for films with a thickness of 50 microns.
- Example 4 Preparation of PETG films containing other liquid additives.
- the technique used was extended without changes to the other additives described in Example 2.
- the concentration of the additives was set at 4%.
- the films obtained, with a thickness of 50 .mu.m +/- 10 .mu.m, showed degradation times of two months, substantially, under the conditions of artificial compost defined above.
- the films obtained are suitable for the packaging of wet products.
- they will not be recommended for the packaging of fatty food products, unless they have the "food quality" label, as is the case, for example, with ethylene glycol di stearate or certain paraffin oils. low molecular weight.
- the stability of the film over time (if it is a film) will be closely related to the conditions of use.
- the migration of the fatty esters is very slow at low temperature for example in the freezer or in the refrigerator but increases in heat. This is a factor to consider in applications.
- EXAMPLE 5 Addition of Another Polyester To the mixture obtained in Example 1, corresponding to PETG containing 5% by weight of TEGDA, 5 to 20% by weight of polyethylene naphthalate (PEN), a thermoplastic polyester product synthesized by Teijin Dupont Films Japan Limited. This mixture leads to granules that can form films.
- the films obtained are still biodegradable, in addition the glass transition temperature rises from 10 to 50 ° C according to the proportion of PEN. They will therefore be more stable to heat.
- the degradation times vary from 1 month (5% PEN) to three months (20% PEN) for films with a thickness of 50 microns.
- the films obtained do not show no sign of degradation after a period of five months under the conditions of the previous tests.
- These molding or injection-molding products can also give thin films (from 10 to 100 microns) but which lack flexibility. Thick films (of the order of mm) can be thermoformed.
- a granulate is prepared using the CLEXTRAL BC21 twin-screw extruder.
- PETG is introduced, in the other the Atofma reference 1008FE24 low density polyethylene (PELD), and the TEGDA in the feed well, using a dosing pump, so as to obtain granules of final composition by weight: PETG 75, PELD 20, TEGDA 5.
- PELD low density polyethylene
- Orevac 18630 (Atofina), an ethylene / methyl acrylate random copolymer, composed of 20% by weight of methyl acrylate.
- Orevac is used to ensure better compatibility between various polymers including PET / PRTG, PS, PE, EVA, EVOH.
- the final proportions, by weight are the following: PETG 70, PELD 20, TEGDA 5, Orevac 5.
- the films are prepared as in Example 3 using the granules defined above.
- the following temperature profile ( 0 C) was used: 180 (hopper), 180, 170, 160 the
- the films obtained, with a thickness of 50 ⁇ m +/- 10 ⁇ m, are much more flexible than those obtained in Examples 3, 4, 5.
- Films composed of PETG and 20% PELD were prepared for comparison. In the absence of TEGDA, the films obtained show no sign of degradation after a period of five months under the conditions of the previous tests.
- Evatane is a random copolymer of ethylene and vinyl acetate marketed by Atofina.
- the Evatane 28-03 used contains 28% vinyl acetate.
- a granulate is prepared using the CLEXTRAL BC21 twin-screw extruder.
- PETG is introduced, in the other the EVA and TEGDA so as to obtain granules of final composition by weight: * PETG 75, EVA 20, TEGDA 5. * PETG 50, EVA 35, TEGDA 5.
- the films are prepared as in Example 3. In both cases, the following temperature profile ( 0 C) was used: 160 (hopper), 160, 150, 140 (degassing), 150, 170, 170, 190 (Faculty). The rotational speed of the screw is 70 revolutions per minute.
- L ⁇ vatane® is not spontaneously biodegradable, but when the other elements of the formulation have been severely degraded, its degradation then becomes possible as has been observed with films treated under the preceding conditions with degradation times varying from two months. (10% Evatane®) at four months (30% Evatane®) for 50 micron films. Note that Evatane® migrates poorly in the macromolecular matrix, but the whole remains biodegradable. In fact, the microorganisms of the environment can hydrolyze the acetic ester functions of Evatane®, oxidize the alcohols to ketone functions and finally cut the macromolecular chain into numerous degradable fragments.
- Films composed of PETG and 20% EVA were prepared for comparison. In the absence of TEGDA, the films obtained show no sign of degradation after a period of five months under the conditions of the previous tests.
- Example 6 a granulate is prepared using the CLEXTRAL BC21 twin-screw extruder.
- PETG containing 4% Loxiol or pure PETG, in the other pure EVA or a mixture of granules of EVA and Orevac granules according to the following compositions, expressed by weight:
- the films are prepared as in Example 3. In both cases, the following temperature profile (° C) was used: 160 (hopper), 160, 150, 140 (degassing), 150, 170, 170, 190 (Faculty). The rotational speed of the screw is 70 revolutions per minute.
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007514030A JP2008501815A (ja) | 2004-06-04 | 2005-06-03 | 生分解性熱可塑性組成物およびその製造方法 |
EP05775268A EP1776414A1 (fr) | 2004-06-04 | 2005-06-03 | Composition thermoplastique biodegradable et procede de preparation |
US11/628,437 US20080281026A1 (en) | 2004-06-04 | 2005-06-03 | Biodegradable Thermoplastic Composition and Method for the Preparation Thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0406084 | 2004-06-04 | ||
FR0406084A FR2871166B1 (fr) | 2004-06-04 | 2004-06-04 | Composition thermoplastique biodegradable et procede de preparation |
Publications (1)
Publication Number | Publication Date |
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WO2006003280A1 true WO2006003280A1 (fr) | 2006-01-12 |
Family
ID=34945967
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/FR2005/001363 WO2006003280A1 (fr) | 2004-06-04 | 2005-06-03 | Composition thermoplastique biodegradable et procede de preparation |
Country Status (5)
Country | Link |
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US (1) | US20080281026A1 (fr) |
EP (1) | EP1776414A1 (fr) |
JP (1) | JP2008501815A (fr) |
FR (1) | FR2871166B1 (fr) |
WO (1) | WO2006003280A1 (fr) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2920234A4 (fr) * | 2012-11-16 | 2016-07-06 | Rhodia Operations | Composition polymère thermoplastique comprenant un sel hypophosphite de métal alcalin |
KR102031278B1 (ko) * | 2019-02-07 | 2019-10-14 | 권상도 | 친환경 비닐의 제조방법 및 이에 의해 제조된 친환경 비닐 |
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FR2611732A1 (fr) * | 1987-03-06 | 1988-09-09 | Tecnocolor Sas Celebrano A C | Procede pour obtenir la biodegradabilite de produits jetables en matieres plastiques |
JPH04146953A (ja) * | 1990-10-09 | 1992-05-20 | Agency Of Ind Science & Technol | プラスチックの生分解性制御方法 |
US5540962A (en) * | 1992-10-16 | 1996-07-30 | Leonard Pearlstein | Degradable package for containment of liquids |
US5753782A (en) * | 1993-06-02 | 1998-05-19 | Zeneca Limited | Polyester composition |
WO1999023146A1 (fr) * | 1997-10-31 | 1999-05-14 | Monsanto Company | Compositions de polyhydroxyalcanoates et leurs procedes d'utilisation dans la production de pieces moulees polymeres |
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US4284671A (en) * | 1979-05-11 | 1981-08-18 | Clopay Corporation | Polyester compositions for gas and moisture barrier materials |
CH671961A5 (fr) * | 1987-02-27 | 1989-10-13 | Amrotex Ag | |
US5352716A (en) * | 1992-12-16 | 1994-10-04 | Ecostar International, L.P. | Degradable synthetic polymeric compounds |
EP0723572B1 (fr) * | 1993-10-15 | 1999-12-08 | H.B. Fuller Licensing & Financing, Inc. | Adhesifs thermofusibles biodegradables/recyclables en compost constitues de polyester d'acide lactique |
JPH09238579A (ja) * | 1996-03-05 | 1997-09-16 | Sangyo Gijutsu Kenkyusho:Kk | 生分解性成形材料 |
JP4959057B2 (ja) * | 1999-03-12 | 2012-06-20 | ポリプラスチックス株式会社 | ポリエステル樹脂組成物 |
US6482872B2 (en) * | 1999-04-01 | 2002-11-19 | Programmable Materials, Inc. | Process for manufacturing a biodegradable polymeric composition |
JP2003005608A (ja) * | 2000-10-18 | 2003-01-08 | Ricoh Co Ltd | 像担持体上の付着物除去方法およびその方法を用いる画像形成装置 |
CN1363625A (zh) * | 2001-11-15 | 2002-08-14 | 天津丹海股份有限公司 | 生物降解树脂的生产方法 |
JP2003171474A (ja) * | 2001-12-07 | 2003-06-20 | C I Kasei Co Ltd | 生分解性フィルム |
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JP2004359892A (ja) * | 2003-06-06 | 2004-12-24 | Sakamoto Yakuhin Kogyo Co Ltd | ポリエステル樹脂組成物 |
-
2004
- 2004-06-04 FR FR0406084A patent/FR2871166B1/fr not_active Expired - Fee Related
-
2005
- 2005-06-03 EP EP05775268A patent/EP1776414A1/fr not_active Withdrawn
- 2005-06-03 WO PCT/FR2005/001363 patent/WO2006003280A1/fr active Application Filing
- 2005-06-03 US US11/628,437 patent/US20080281026A1/en not_active Abandoned
- 2005-06-03 JP JP2007514030A patent/JP2008501815A/ja active Pending
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JPH04146953A (ja) * | 1990-10-09 | 1992-05-20 | Agency Of Ind Science & Technol | プラスチックの生分解性制御方法 |
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Also Published As
Publication number | Publication date |
---|---|
JP2008501815A (ja) | 2008-01-24 |
EP1776414A1 (fr) | 2007-04-25 |
FR2871166A1 (fr) | 2005-12-09 |
US20080281026A1 (en) | 2008-11-13 |
FR2871166B1 (fr) | 2006-12-01 |
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