New! View global litigation for patent families

WO2002059201A1 - Binary mixtures of biodegradable aliphatic polyesters and products obtained from these - Google Patents

Binary mixtures of biodegradable aliphatic polyesters and products obtained from these

Info

Publication number
WO2002059201A1
WO2002059201A1 PCT/EP2002/000761 EP0200761W WO02059201A1 WO 2002059201 A1 WO2002059201 A1 WO 2002059201A1 EP 0200761 W EP0200761 W EP 0200761W WO 02059201 A1 WO02059201 A1 WO 02059201A1
Authority
WO
Grant status
Application
Patent type
Prior art keywords
acid
film
mixture
according
polyesters
Prior art date
Application number
PCT/EP2002/000761
Other languages
French (fr)
Other versions
WO2002059201A8 (en )
Inventor
Catia Bastioli
Tredici Gianfranco Del
Italo Guanella
Giovanni Floridi
Roberto Ponti
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

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediatly laminated while in semi-molten state
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38Packaging materials of special type or form
    • B65D65/46Applications of disintegrable, dissolvable or edible materials
    • B65D65/466Bio- or photodegradable packaging materials
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • DTEXTILES; PAPER
    • D01NATURAL OR ARTIFICIAL THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2270/00Resin or rubber layer containing a blend of at least two different polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/716Degradable
    • B32B2307/7163Biodegradable
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/726Permeability to liquids, absorption
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2367/00Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00Adhesive articles, e.g. adhesive tapes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2437/00Clothing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00Containers; Receptacles
    • B32B2439/40Closed containers
    • B32B2439/46Bags
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00Containers; Receptacles
    • B32B2439/70Food packaging
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2451/00Decorative or ornamental articles
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10Bio-packaging
    • Y02W90/11Packing containers made from renewable resources
    • Y02W90/12Packing containers made of bio-plastics
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10Bio-packaging
    • Y02W90/11Packing containers made from renewable resources
    • Y02W90/13Biodegradable packaging containers

Abstract

A biodegradable mixture obtained by melt mixing polyesters comprising: (A) an aliphatic polyesters of the kind polyhydroxyacid or diaic/diol and their copolymer; (B) a polymer of lactic acid comprising L or D polylactic acid, L, D-polylactic, meso polylactic acid and lactic acid copolymers with hydroxyacids or lactones thereof containing at least 75% of L-lactic or D-lactic acid in which the concentration by weight of A with respect to (A+B) is in the range 30-60% and in which the sum of the fusion entalpies ΔHA and ΔHB of the two polyesters in the mixture is greater than the normalized sum of the fusion entalpies Δ1 and ΔH2 of the aliphatic polyesters prior to melt mixing, the fusion entalpy converted to the polylactic acid-family polymer when the temperature of the film is raised being greater than 35 J/g.

Description

Binary mixtures of biodegradable aliphatic polyesters and products obtained from these

The present invention relates to biodegradable mixtures comprising at least two aliphatic polyesters in proportions such that it is possible to obtain a film, by blowing or casting, provided with improved water barrier properties with respect to individual polyesters, of high rigidity, transparency and biodegradability as well 'as' solid and expanded (foamed) sheets and associated thermoformed products with optimum barrier properties and rigidity.

Such composite materials are particularly suitable for the food packaging sector for rigid films which easily form a skin, expanded and solid containers, dishes and casting etc.

Prior Art

Conventional polymers such as polystyrene, polyethylene^ terephthalate and similar are characterised not only by an excellent rigidity, but also by good barrier properties against water and. by good transparency. These polymers are used in the packaging sector in general, and in food packaging in particular, as well as ' in the sector of disposable dishes such as plates, cups and cutlery. Their low biodegradability and the difficulty of recovering the different starting plastics in a sufficiently differentiated manner upon recycling has however created an increasing problem of disposal in recent decades.

Polymers such as L-polylactic acids, D,L-polylactic acids, D- polylactic acids and their co-polymers are biodegradable thermoplastic materials from renewable sources; they are transparent with excellent resistance to fungi and therefore suitable for packaging food as well as preservation of their organoleptic characteristics. On the other hand they biodegrade slowly in the soil and, in compost, degrade quickly only at high temperatures. The greatest limitation, however, lies in the low processability, upon recycling of waste, and also in that for many applications the permeability to water is too high. In food packaging there is moreover a not insignificant difficulty of welding.

If, on the other hand, aliphatic polyesters constituted predominantly of monomers from renewable sources starting from diacidic diols are considered, these have the limitation that their rigidity is too low and their water permeability is too high. For th s reason products prepared from these resins are also inadequate as rigid materials for packaging.

Binary mixtures of polylactic acid and aliphatic polyesters have constituted the subject of many patents. In particular, European Patent EP-0 980 894 Al '(Mitsui Chemical) claims a significant improvement in the tear strength and balance of film based on a blend of polylactic acid and other polyesters such as polybutylene succinate, with a melting point of between 80 and 250° C, by introducing a plasticiser into the blend. This, however, gives a non-transparent film with, in any event, very modest strength of the order of 120g in accordance with the JIS P8116 method. The presence of a plasticiser, moreover, places limitations on contact with food, and the disadvantage of ageing phenomena.

US Patent US 5,883,199 relates to binary mixtures of polylactic acid and polyester with the polyester forming a continuous or co-continuous phase and the polylactic acid content lying between 10 and 90%. Such mixtures, in accordance with the indicated examples, do not show significant reduction in the permeability to water or steam.

EP-1 033 383 relates to a biodegradable film comprising a polylactic acid-family polymer and other aliphatic polyester than the polylactic acid-family polymer charactherized in that the heat for fusion converted to the polylactic acid- family polymer when the temperature of the film is raised is 35 J/g or under. Such patent does not deal with the problem of improving the barrier properties against water of the biodegradable film.

Subject of the invention

Starting from the problem of finding a material able to combine properties of transparency, rigidity and water barrier it has now surprisingly been found that by combining a polymer of polylactic acid with aliphatic polyesters of the kind polyhydroxyacid or diacid/diol or their copolymers in specific ratios as described hereinafter there is a critical range of compositions in which it is possible to obtain, entirely unexpectedly, a significantly lower permeability to water with respect to the individual polymers, as well as modulus of elasticity in tension greater than any envisaged from the Halpin/Tsai mixture rule, and an optimum transparency.

Description of the invention

The invention relates to a biodegradable mixture obtained by melt mixing polyesters comprising: (A) An aliphatic polyester of the kind polyhydroxyacid, with the exclusion of polymers of lactic acid, or diacid/diol or their copolymers with modulus of elasticity lying between 400 and 900 MPa and breaking elongation greater than 200%, more preferably greater than 300%, on blown film of about 25- 30μm, average ponderal molecular weight greater than 55,000 and more preferably greater than 65,000, and melting point lying between 40 and 95° C; preferably between 55 and 85° C and more preferably between 57 and 79° C;

(B) A polymer of lactic acid comprising L or D polylactic acid, L,D-polylactic, meso polylactic acid and lactic acid copolymers with hydroxyacids or lactones thereof containing at least 75% of L-lactic or D-lactic acid with average ponderal molecular weight higher than 70,000 and with a modulus of elasticity greater than 1500 MPa;

in which the concentration by weight of A with respect to (A+B) is in the range 30-60% and in which blown film of a thickness of 25 - 30 μm has modulus of elasticity greater than 1400MPa, permeability to water comprised form 170 to 40 g30μm/m224h, a transmittance measured at the entrance port lying between 90 and 95% and in which the sum of the fusion entalpies ΔHA and ΔHB of the two polyesters in the mixture is greater than the normalized sum of the fusion entalpies ΔHi and ΔH2 of the aliphatic polyesters prior to melt mixing, the fusion entalpy converted to the polylactic acid polymer being greater than 35 J/g .

For normalised sum it is meant the sum obtained by multiplying the ΔHi and ΔH2 fusion entalpies for the percentage divided by 100 of the two polyesters present in the mixture.

The increase of the fusion entalpies ΔHA + ΔHB of the two polyesters in the mixture with respect to their normalised sum ΔHi + ΔH2 shows an unexpected increase of cristallinity in the mixture which is the cause of the surprisingly very low value of the permeability to water exibited by the composition according to the invention.

The mixture of biodegradable polyesters according to the invention is obtained from a process which involves working in a twin screw or single screw extruder in temperature conditions between 140 and 200° C, performing the two steps of the mixing process and film forming together or separately. Film forming separate from the mixing process is achieved with conventional machines for the extrusion of low or high density polyethylene with a temperature profile in the range between 100 and 200° C, and it is possible to obtain films having thicknesses lying between 5 and 250μm. Film forming at temperatures lying between 150 and 200° C is preferred.

Film with thicknesses of 25-30μm has characteristics of transparency lying in the range 35-80% for the source transmittance, and in the interval 90-95% for the entry point transmittance. The permeability to steam or water at 38° C with a relative humidity on one side of the film of 10%, to obtain a Δ relative humidity of 90% in static conditions, lies between 170 and 40 grams of water referred to 30μm of thickness of the film which passes through a square metre of surface in twenty-four hours (g30μm/m224h) and more preferable between 120 and 70 grams (g30μm/m224h) . The individual polymers constituting the mixture according to the invention, in the same film conditions, give values of permeability lying between 200 and 800 gr. (g30μm/mz24h) .

The tensile properties in the longitudinal film direction in terms of modulus of elasticity measured according to ASTM 882 exceed 1000 MPa and preferably 1400 MPa.

In the mixing phase polymers of type A with MFI (150° C, 2.16 kg) lying between 1 and 10 dg/min are preferred and polymers C with MFI (190° C, 2.16 kg) lying between 2 and 30 dg/min are preferred.

As above specified, polymer (A) includes polyhydroxyacids, with the exclusion of polymers of lactic acid, and/or dicarboxylic aliphatic acids/ aliphatic diols polyesters and their copolymers .

Typical monomers of the polyhydroxyacids include glycolic acid, 3-hydroxybutyric, 4-hydroxybutyric, 3-hydroxyvaleric, 4-hydroxyvaleric, and 6-hydroxycaproic acid and further includes cyclic esters of hydroxycarboxylic acids such as glycolides, dimers of glycolic acid, ε-caprolactone and 6- hydroxycaproic acids. Preferred monomer is ε-caprolactone. Mixtures of these acids can be used. These acids are also suitable as comonomers for the diacid/diol polyesters.

Examples of diacids are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pi elic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, undecandioic acid, and dodecandioic acid. Azelaic acid, sebacic acid and brassylic acid are preferred. Specific glycols are ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,2- and 1,3- propylene glycol, 1, 3-butandiol, 1,4-butandiol, 3-methyl - 1,5-pentandiol, 1, 6-hexandiol, 1, 9-nonondiol, dipropylene glycol, 1, 11-undecandiol, 1, 13-tridecandiol, neopentyl glycol, polytetramethylene glycol, 1, 4-cyclohexane dimethanol and cyclohexane diol . Mixtures of these compounds can be used.

All the compounds discussed above are combined in such a way

/ as to form polyesters with mechanical characteristics of tensile resistance to elongation greater than 300% and modulus of elasticity lying between 400 and 900 MPa on blown films of at least 30 μm thickness and with a melting point between 40 and 95° C, preferably between 55 and 85° C and more preferably between 57 and 79° C. Particularly preferred polyesters are poly-ε-caprolactone and its copolyesters .

Also included in polymers of type A are polyamide polyesters where the polyester part is as described above and the polyamide part can be caprolactam, and aliphatic diamine such as hexamethylene diamine or even an amino acid. The type A polyesters can also contain aromatic diacids in quantities less than 5 moles%. Polycarbonates also belong to polymers of type A.

The polyesters can be polymerised via polycondensation or, as in the case of glycolides and lactones, by ring opening as known in the literature. Morever, polyesters can be branched polymers with the introduction of polyfunctional monomers such as glycerine, epoxyoized soya oil, trimethylpropane and the like or polycarboxylic acids such as butantetracarboxylic acid.

egrading with isocyanates can take place in the molten state at the end of the polymerisation reaction or in the extrusion phase, or in the solid state as described in the Novamont Patent WO 99/28367. The two types of polymers A and B can also have additives such as chain extenders or cross linking agents of the type described above in the mixing phase.

Ratios between polymer A and polymer B different from those described for the mixtures according to the present invention give rise to products not having sufficient barrier properties and, in the case of excessively high content of polymer A, excessively low modulus of elasticity.

The material obtained from the mixture of two polymers A and B has no need for plasticisers which create problems of migration especially for food packaging. However, quantities of plasticisers below 5% with respect to polymers A + B can be added.

Various additives can also be incorporated in the mixture, such as antioxidants, UN stabilisers, stabilisers against heat and hydrolysis, flame retardants, slow release agents, organic and inorganic fillers such as, for example, natural fibres, anti-static agents, humectants, colorants and lubricants .

In particular, in the production of blown or cast film the following can be added: silica, calcium carbonate, talc, kaolin, kaolinite, zinc oxide, wollastonites, various hydrotalcites and in general lamellar inorganic substances whether or not functionalised with organic molecules capable of delamellating in the mixing phase with the polymeric mixture or with one of the individual polymers of the mixture to give nanocomposites with improved antiblocking and barrier properties . The various inorganic substances can be used in mixtures or with individual products. The concentration of the inorganic additives is generally between 0.05 and 30%, preferably between 0.5 and 20%.

To improve the film-forming characteristics there can be added amides of aliphatic acids such as oleamide, stearamide, erucamide, behenamide, N-oleylpalmitamide, N-stearylerucamide and other amides, salts of fatty acids such as aluminium, zinc or calcium stearate and the like. The quantities of these additives vary from 0.05 to 7 parts and preferably between 0.1 and 5 parts of the polymer mixture.

The mixture thus obtained can be transformed into a film by blowing or extrusion through a flat head, can be extruded as a solid sheet or a foamed or expanded sheet and then heat formed. The films are transparent, have a high resistance to water (water barrier) with respect to the biodegradable starting materials according to CEN 13432, and moreover have a sufficient rigidity for food packagings which require rigid films. The film is weldable and can be obtained in thickness up to 5μm by blowing or casting.

In the non-food field the films obtained with the mixture according to the invention are excellent for applications such as films for adhesive tape, tapes for nappies, for ornamental coloured tapes, for adhesive tapes of different form and use and moreover in applications such as bags for clothing, or film for wrapping flowers, plants and gift objects.

In the food field the films obtained with the mixture according to the invention are excellent for applications such as packets for dried products (biscuits, crackers, crisps, chipsters and the like) , chocolate, cheese, meat, vegetables etc. and in applications such as joining and tear strip films for sealing containers.

The films advantageously find use also in agriculture or in any event for outside use and can contain ON stabilisers in the form of individual films or coextrusions with films having a low modulus, as in the case of starch-based materials, to give improved UN resistance, improved barrier properties, and a different rate of degradation in the atmosphere and in the soil.

The films can moreover be surface treated with aluminium or silica or others, and can be laminated with other materials so as to combine different characteristics (barrier to oxygen and/or to water, peelability, connectability etc) . For these cases, as particularly advantageous examples of practical applications, one can mention containers for yoghurt, cheese, meat, bread, biscuits, potatoes and snacks in general, bowls for industrial use, and containers for fragile objects such as eggs.

The films can advantageously be used as the weldable component of a multi-layer film composed of at least one layer of polylactic acid or other polyester, non-destructured starch (and its blends with synthetic and natural polymers) or as components of a multi-layer with aluminium and other materials or with a vacuum metalised layer with aluminium, silica and other inorganic materials. The multi-layers can be obtained by coextrusion or by lamination or by extrusion coating, if one layer is paper or other material which does not melt between 100 and 200° C.

The biodegradable polymer mixtures according to the invention can moreover find advantageous use in the form of products obtained using other techniques than film forming. For example, they can be used to obtain fibres for textiles and non-woven textiles, or for fishing nets. Moreover, the non- woven fabric can be used in the sanitary sector for nappies, sanitary towels etc. The fibres can also be utilised as weldable reinforcing fibres in special papers.

The material can also be utilised with success also for the production of sheets for thermoforming, extruded or coextruded with other layers of polymers such as polylactic acid or other polyesters or polyamides or materials based on starch then thermoformed to form containers for food, agriculture and others. The material can be used for injection moulding of containers, cutlery or other things, and has a very high speed of crystallisation and a very high crystallinity.

The material can also have polymeric additives such as polyethylene waxes and polypropylene, PET and PTB, polystyrene, copolymers of ethylene and propylene with functional carboxylic groups, carboxylate, methacrylate, acrylate or hydroxylic groups or else combined with these polymers in coextrusions, coinjections or the like. The material can be utilised as a matrix in the blend with destructured starch according to the processes described in Novamont Patents (EP-0 327 505, EP-0 539 541, EP-0 400 532, EP-0 413 798, EP-0 965 615) with the possibility of forming complexes with the starch or simply utilising the destructured starch, converted and/or complexed as a submicronic filler for the polyester.

They can be used as coating films for biodegradable expanded materials based on polyesters, polyamides, thermoplastic starch and complexed starch or simply blends of starch with other polymers or with the material of the present invention.

The material, on its own or in mixture with starch or other polymers can be obtained as an expanded material to form containers for fruit and vegetables, meat, cheese and other food products, or containers for fast food. It can also be obtained in the form of expanded particles which can be agglomerated for industrial packaging or in the form of injected foam.

The mixture according to the invention will now be described with the following non-limititive examples.

Examples

Example 1

Polymers constituting the mixture:

Aliphatic polyester: poly-ε-caprolactone (TONE 787 Union

Carbide)

Poly L-lactic acid with a D-lactic content of 6%: 4040 Cargill .

Formed into a film on a Ghioldi machine:

Diameter = 40mm, L/D = 30; rpm=45; die: diameter = 100mm; air gap = 0.9mm; land = 12; flowrate = 17 kg/h; temperature profile: 120-150-190x2; temperature filter = 190x2; head temperature = 190x2.

Film: width = 400mm; thickness = 25μm.

The determination of the values of transmittance, both at the source port (TSOOECE) and at the entry port (Tentr) was effected by means of a HAZEGUARD SYSTEM X -211.

The values of breaking load (α) , elongation at break (ε) and modulus of elasticity (E) were determined in accordance with the ASTM D 882-91 by means of an INSTRON 4502 instrument.

The values of permeability, expressed in g30μm/m224h were determined at 38° C with a relative humidity of 10% on one side of the film to guarantee a Δ humidity equal to 90% in static conditions with cups of diameter 61.8mm and a depth of 28.5mm filled with H20 to a height of 10mm from the bottom. The cups were put in a climatic cell positioned within a perforated box which guarantees the absence of air currents within it which may cause possible turbulence phenomena on the surface of the specimen, and thus an uncontrolled increase in the exchange efficiency. The values found identify the grams of water referred to 30μm of thickness of film which passed through a square metre of surface in twenty-four hours.

Comparative examples 2-6

Examples 2 and 2a refer to the pure polylactic acid respectively with and without 0,3% erucamid (slipping agent) .

Examples 3-6 were made with BIONOLLE a commercially available aliphatic polyester: examples 3-4 with BIONOLLE 1903 (polybutylensuccinate homopolymer) and example 5-6 with Bionolle 3001 (polybutylensuccinate-adipate copolymer) . These examples show permeability values outside the range of the compositions according to the present invention.

Results of the tests conducted are plotted in Table 1.

Table 2 shows the ΔH values referrred to the polyesters prior to melt mixing (ΔHx and ΔH2) and to the polyesters in the mixture (ΔHA and ΔHB) . The table refers to the compositions of examples 1, 4 and 6. Example 1 is according to the invention whereas examples 4 and 6 refer respectively to Bionolle 1903 and Bionolle 3001 .

The values have been determined on films of about 25-30 μm. A Perkin Elmer DSC 7 analyzer was used. ΔHX and ΔH2 are the fusion entalpy values of the polyesters . ΔHX + ΔH2 is the sum of the heat fusion values normalized in relation to the mixtures percentages. The values are expressed in J/g. The Differential Scanning Calorimetry has been performed raising the temperature at a ratio of 20°C per minute.

According to example 1 the fusion entalpy converted to the polylactic acid polymer is 39.8.

TABLE

TABLE 2

Claims

1. A biodegradable mixture obtained by melt mixing polyesters comprising:
(A) An aliphatic polyester of the kind polyhydroxyacid, with the exclusion of polymers of lactic acid, or diacid/diol and their copolymers said polyester having modulus of elasticity comprised from 400 to 900 MPa and breaking elongation greater than 200% on blown film of about 25-30μm, average ponderal molecular weight greater than 55,000 and melting point from 40 to 95° C;
(B) A polymer of lactic acid comprising L or D polylactic acid, L,D-polylactic, meso polylactic acid and lactic acid copolymers with hydroxyacids or lactones thereof containing at least 75% of L-lactic or D-lactic acid with average ponderal molecular weight higher than 70,000 and with modulus of elasticity greater than 1500 MPa; in which the concentration by weight of A with respect to (A+B) is in the range 30-60% and blown films of thicknesses of 25 - 30 μm have modulus of elasticity greater than 1400 MPa, permeability to water comprised from 170 to 40 g30μm/m224h and in which the sum of the fusion entalpies ΔHA and ΔHB of the two polyesters in the mixture is greater than the normalized sum of the fusion entalpies ΔHX and ΔH2 of the aliphatic polyesters prior to melt mixing, the fusion entalpy converted to the polylactic acid polymer being greater than 35 J/g.
2 . A mixture according to Claim 1, in which the blown film obtained from mixtures of polymers (A) and (B) has and a transmittance at the entrance port lying between 90 and 95%.
3. A mixture according to the preceding claims in which the hydroxy acid monomer of the polyhydroxyacid comprises glycolic acid, 3-hydroxybutyric, 4-hydroxybutric, '3- hydroxyvaleric, 4-hydroxyvaleric, 6-hydroxycaproic, and further includes cyclic esters of hydroxycarboxylic acids such as glycolides, dimers of glycolic acid, ε-caprolactone and 6-hydroxycaproic acid.
4. A mixture according to the preceding claims, in which the polyhydroxyacid is poly-ε-caprolactone or its copolymers.
5. A mixture according to Claims 1-2, in which the diacid in the diacid/diol polyester is sebacic acid, brassylic acid and azelaic acid or mixtures therof .
6. A mixture according to Claim 5 in which the diol in the diaci/diol polyester is ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1-2 and 1-3 propylene glycol, 1, 3-butandiol, 1,4-butandiol, 3-me hyl- 1, 5-pentandiol, 1, 6-hexandiol. , 1-9 nonandiol, dipropylene glycol, 1, 11-undecandiol, 1, 13-tridecandiol, neopentyl glycol, polytetramethylene glycol and 1, 4-cyclohexane dimethanol , cyclohexane diol or mixtures of these .
7. A mixture according to any preceding claim containing plasticisers in quantities less than 5% by weight with respect to the quantity of aliphatic polyester and polymer of the lactic acid.
8. A film produced by blowing or flat head extrusion with mixtures of biodegradable polymers according to any preceding claim.
9. A film according to Claim 8, in which the mixture comprises one or more inorganic additives such as silica, calcium carbonate, talc, kaolin, kaolinite, oxide of zinc, wollastonite, hydrotalcite, lamellar inorganic substances functionalised or not with organic molecules capable of delamellating in the mixing phase with the polmeric mixture or with one of the individual polymers of the mixture to give nanocomposites .
10. A film according to Claim 9, in which the concentration by weight of inorganic additives in the mixture lies between 0.05 and 30.
11. Packets for food or industrial products and clothing, adhesive tapes, tapes for nappies, coloured ornamental tapes, adhesive tapes of different form, film for packaging flowers, plants and gift items, produced from film according to any of Claims 8 to 10.
12. Bags and films for dry products such as bread, biscuits, crackers, crisps, chipsters, chocolate, cheese, meat, vegetables, welding and tear tape, and film for sealing containers, produced from film according to any of Claims 8 to 10.
13. Film according to any of Claims 8 to 10 surface treated with aluminium or silica or laminated.
14. Film according to any of Claims 8 to 10 as component of multi-layer film composed of at least one layer of polylactic acid or other polyester or destructured or non-destructured starch and its blends with synthetic and natural polymers or components of the multi-layer film with aluminium and other materials or with a vaccu -metalised layer with aluminium, silica and other inorganic materials.
15. Fibres for woven and non-woven textiles or for fishing nets produced with mixtures according to any of Claims 1 to 7.
16. Sheets for ther oforming, extruded or coextruded with other layers of polymers then thermoformed into trays for food, agricultural products with biodegradable polymeric mixtures according to any of Claims 1 to 7.
17. Containers for yoghurt, cheese, meat, biscuits, crisps, snacks, trays for industrial use, containers for fragile objects, produced from sheet according to Claim 16.
18. Containers, cutlery, disposable objects, injection moulded from biodegradable polymeric mixtures according to any of Claims 1 to 7.
19. Foam sheet produced with biodegradable polymeric mixtures according to any of Claims 1 to 7 and formed into containers for food such as meat, cheese, vgetables, drinks, containers for fast food and for the industrial sector.
20. Agglomerable expanded particles produced from biodegradable polymeric mixtures according to Claims 1 to 7 for packages for use in the industrial sector.
21. Use of the biodegradable mixture according to any of claims 1 to 7 for applications requiring low water permeability values.
PCT/EP2002/000761 2001-01-25 2002-01-25 Binary mixtures of biodegradable aliphatic polyesters and products obtained from these WO2002059201A8 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
ITTO20010061 2001-01-25
ITTO2001A000061 2001-01-25

Publications (2)

Publication Number Publication Date
WO2002059201A1 true true WO2002059201A1 (en) 2002-08-01
WO2002059201A8 true WO2002059201A8 (en) 2002-11-14

Family

ID=11458439

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2002/000761 WO2002059201A8 (en) 2001-01-25 2002-01-25 Binary mixtures of biodegradable aliphatic polyesters and products obtained from these

Country Status (1)

Country Link
WO (1) WO2002059201A8 (en)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004076582A1 (en) * 2003-02-21 2004-09-10 Metabolix Inc. Pha blends
GB2402393A (en) * 2003-06-02 2004-12-08 Cortec Corp Biodegradable bag
WO2005085351A1 (en) * 2004-02-27 2005-09-15 Cereplast, Inc. Biodegradable poly(lactic acid) polymer composition and films, coatings and products comprising biodegradable poly(lactic acid) polymer composition
WO2006010062A1 (en) * 2004-07-09 2006-01-26 E.I. Dupont De Nemours And Company Sulfonated copolyetherester compositions from hydroxyalkanoic acids and shaped articles produced therefrom
EP1635410A1 (en) * 2003-05-16 2006-03-15 Matsushita Electric Industrial Co., Ltd. Battery package and process for producing the same
WO2007092417A1 (en) * 2006-02-07 2007-08-16 Tepha, Inc. Toughened polylactic acid polymers and copolymers
WO2007099427A1 (en) * 2006-02-28 2007-09-07 Cereplast, Inc. Biodegradable nano-polymer compositions, i.e. compositions including mineral nanoparticles and poly(lactic acid) polymer and biodegradable articles made thereof
WO2008037744A2 (en) * 2006-09-27 2008-04-03 Novamont S.P.A. Biodegradable multiphase compositions based on starch
US7492326B1 (en) 2003-06-02 2009-02-17 Cortec Corporation Biodegradable radio frequency identification cards
EP2300645A2 (en) * 2008-07-16 2011-03-30 Wright & McGill Co. Biodegradable polyester copolymers
CN101445651B (en) 2008-12-26 2011-06-15 扬州大学 Bicontinuous biomacromolecule ternary nanometer composite material and preparation method thereof
US8961591B2 (en) 2008-08-07 2015-02-24 Tepha, Inc. Polymeric, degradable drug-eluting stents and coatings
US9328239B2 (en) 2010-05-17 2016-05-03 Metabolix, Inc. Toughening polylactic acid with polyhydroxyalkanoates
US9353258B2 (en) 2012-06-05 2016-05-31 Metabolix, Inc. Low glass transition polyhydroxyalkanoates for modification of biodegradable polymers
US9592325B2 (en) 2006-02-07 2017-03-14 Tepha, Inc. Polymeric, degradable drug-eluting stents and coatings
US9808017B2 (en) 2011-02-25 2017-11-07 Kraft Foods R&D, Inc. Food product with a moulded body

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2057668A1 (en) * 1991-12-13 1993-06-14 Speros P. Nemphos Degradable foam
JPH0624501A (en) * 1992-07-07 1994-02-01 Mitsui Toatsu Chem Inc Container of recycled waste paper
WO1994007941A1 (en) * 1992-10-02 1994-04-14 Cargill, Incorporated Melt-stable lactide polymer films and processes for manufacture thereof
JPH09272789A (en) * 1996-04-02 1997-10-21 Mitsubishi Chem Corp Aliphatic polyester composition
JPH1024518A (en) * 1996-07-10 1998-01-27 Mitsubishi Plastics Ind Ltd Polylactic biodegradable gas barrier film
US5866634A (en) * 1995-09-25 1999-02-02 Shin-Etsu Chemical Co., Ltd Biodegradable polymer compositions and shrink films

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2057668A1 (en) * 1991-12-13 1993-06-14 Speros P. Nemphos Degradable foam
JPH0624501A (en) * 1992-07-07 1994-02-01 Mitsui Toatsu Chem Inc Container of recycled waste paper
WO1994007941A1 (en) * 1992-10-02 1994-04-14 Cargill, Incorporated Melt-stable lactide polymer films and processes for manufacture thereof
US5866634A (en) * 1995-09-25 1999-02-02 Shin-Etsu Chemical Co., Ltd Biodegradable polymer compositions and shrink films
JPH09272789A (en) * 1996-04-02 1997-10-21 Mitsubishi Chem Corp Aliphatic polyester composition
JPH1024518A (en) * 1996-07-10 1998-01-27 Mitsubishi Plastics Ind Ltd Polylactic biodegradable gas barrier film

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 9409, Derwent World Patents Index; AN 1994-071624, XP002196362 *
DATABASE WPI Week 9801, Derwent World Patents Index; AN 1998-004290, XP002196361 *
HIDETO TSUJI ET AL: "BLENDS OF ALIPHATIC POLYESTERS.I. PHYSICAL PROPERTIES AND MORPHOLOGIES OF SOLUTION-CAST BLENDS FROM POLY(DL-LACTIDE) AND POLY(EPSILON-CAPROLACTONE)", JOURNAL OF APPLIED POLYMER SCIENCE, JOHN WILEY AND SONS INC. NEW YORK, US, vol. 60, no. 13, 27 June 1996 (1996-06-27), pages 2367 - 2375, XP000634752, ISSN: 0021-8995 *
IANNACE S ET AL: "POLY(3-HYDROXYBUTYRATE)-CO-(3-HYDROXYVALERATE)/POLY-L-LACTIDE BLENDS: THERMAL AND MECHANICAL PROPERTIES", JOURNAL OF APPLIED POLYMER SCIENCE, JOHN WILEY AND SONS INC. NEW YORK, US, vol. 54, no. 10, 5 December 1994 (1994-12-05), pages 1525 - 1535, XP000514124, ISSN: 0021-8995 *
PATENT ABSTRACTS OF JAPAN vol. 1998, no. 05 30 April 1998 (1998-04-30) *
POLYMER DEGRADATION AND STABILITY, vol. 59, 1998, pages 161 - 168, XP004294370 *

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006518799A (en) * 2003-02-21 2006-08-17 メタボリックス インコーポレイティッド Pha blend
EP2241605A3 (en) * 2003-02-21 2012-03-21 Metabolix, Inc. Pha blends
JP4724111B2 (en) * 2003-02-21 2011-07-13 メタボリックス インコーポレイティッド Pha blend
WO2004076582A1 (en) * 2003-02-21 2004-09-10 Metabolix Inc. Pha blends
EP1935945A1 (en) * 2003-02-21 2008-06-25 Metabolix, Inc. PHA Blends
EP1635410A1 (en) * 2003-05-16 2006-03-15 Matsushita Electric Industrial Co., Ltd. Battery package and process for producing the same
EP1635410A4 (en) * 2003-05-16 2010-01-13 Panasonic Corp Battery package and process for producing the same
US7492326B1 (en) 2003-06-02 2009-02-17 Cortec Corporation Biodegradable radio frequency identification cards
GB2402393A (en) * 2003-06-02 2004-12-08 Cortec Corp Biodegradable bag
US6984426B2 (en) 2003-06-02 2006-01-10 Cortec Corporation Biodegradable bag
WO2005085351A1 (en) * 2004-02-27 2005-09-15 Cereplast, Inc. Biodegradable poly(lactic acid) polymer composition and films, coatings and products comprising biodegradable poly(lactic acid) polymer composition
US7193029B2 (en) 2004-07-09 2007-03-20 E. I. Du Pont De Nemours And Company Sulfonated copolyetherester compositions from hydroxyalkanoic acids and shaped articles produced therefrom
WO2006010062A1 (en) * 2004-07-09 2006-01-26 E.I. Dupont De Nemours And Company Sulfonated copolyetherester compositions from hydroxyalkanoic acids and shaped articles produced therefrom
US9592325B2 (en) 2006-02-07 2017-03-14 Tepha, Inc. Polymeric, degradable drug-eluting stents and coatings
WO2007092418A3 (en) * 2006-02-07 2008-08-14 Detlef Behrend Polymeric, degradable drug-eluting stents and coatings
WO2007092417A1 (en) * 2006-02-07 2007-08-16 Tepha, Inc. Toughened polylactic acid polymers and copolymers
US7618448B2 (en) 2006-02-07 2009-11-17 Tepha, Inc. Polymeric, degradable drug-eluting stents and coatings
US8979921B2 (en) 2006-02-07 2015-03-17 Tepha, Inc. Polymeric, degradable drug-eluting stents and coatings
US7927532B2 (en) 2006-02-28 2011-04-19 Cereplast, Inc. Biodegradable nano-polymer compositions and biodegradable articles made thereof
WO2007099427A1 (en) * 2006-02-28 2007-09-07 Cereplast, Inc. Biodegradable nano-polymer compositions, i.e. compositions including mineral nanoparticles and poly(lactic acid) polymer and biodegradable articles made thereof
WO2008037744A3 (en) * 2006-09-27 2008-05-22 Novamont Spa Biodegradable multiphase compositions based on starch
WO2008037744A2 (en) * 2006-09-27 2008-04-03 Novamont S.P.A. Biodegradable multiphase compositions based on starch
US8101253B2 (en) 2006-09-27 2012-01-24 Novamont S.P.A. Biodegradable multiphase compositions based on starch
RU2476465C2 (en) * 2006-09-27 2013-02-27 НОВАМОНТ С.п.А. Biodegradable multiphase starch-based compositions
CN101522797B (en) 2006-09-27 2013-06-05 诺瓦蒙特股份公司 Biodegradable multiphase compositions based on starch
EP2300645A4 (en) * 2008-07-16 2011-10-05 Wright & Mcgill Co Biodegradable polyester copolymers
EP2300645A2 (en) * 2008-07-16 2011-03-30 Wright & McGill Co. Biodegradable polyester copolymers
US8961591B2 (en) 2008-08-07 2015-02-24 Tepha, Inc. Polymeric, degradable drug-eluting stents and coatings
CN101445651B (en) 2008-12-26 2011-06-15 扬州大学 Bicontinuous biomacromolecule ternary nanometer composite material and preparation method thereof
US9328239B2 (en) 2010-05-17 2016-05-03 Metabolix, Inc. Toughening polylactic acid with polyhydroxyalkanoates
US9808017B2 (en) 2011-02-25 2017-11-07 Kraft Foods R&D, Inc. Food product with a moulded body
US9353258B2 (en) 2012-06-05 2016-05-31 Metabolix, Inc. Low glass transition polyhydroxyalkanoates for modification of biodegradable polymers

Also Published As

Publication number Publication date Type
WO2002059201A8 (en) 2002-11-14 application

Similar Documents

Publication Publication Date Title
US5834582A (en) Degradable polymer composition
US7368503B2 (en) Compatibilized blends of biodegradable polymers with improved rheology
US7393590B2 (en) Biodegradable poly(lactic acid) polymer composition and films, coatings and products comprising Biodegradable poly(lactic acid) polymer compositions
US7144632B2 (en) Aliphatic-aromatic polyetherester compositions, articles, films, coating and laminates and processes for producing same
US6756331B2 (en) Lactic-acid base resin composition and molded articles made therefor
US7388058B2 (en) Polyester blend compositions and biodegradable films produced therefrom
US20080027178A1 (en) Article comprising poly(hydroxyalkanoic acid)
US20050171250A1 (en) Aliphatic-aromatic polyesters, and articles made therefrom
US7220815B2 (en) Sulfonated aliphatic-aromatic copolyesters and shaped articles produced therefrom
US6787245B1 (en) Sulfonated aliphatic-aromatic copolyesters and shaped articles produced therefrom
US7172814B2 (en) Fibrous sheets coated or impregnated with biodegradable polymers or polymers blends
US20090234042A1 (en) Transparent blends of polypropylene carbonate
US20080071008A1 (en) Toughened poly(hydroxyalkanoic acid) compositions
US5849374A (en) Compostable multilayer structures, methods for manufacture, and articles prepared therefrom
US6803443B1 (en) Impact modifier and polyester composition containing the modifier
US20040024102A1 (en) Sulfonated aliphatic-aromatic polyetherester films, coatings, and laminates
US7235287B2 (en) Biodegradable laminated sheet
US6312823B1 (en) Compostable multilayer structures, methods for manufacture and articles prepared therefrom
US7193029B2 (en) Sulfonated copolyetherester compositions from hydroxyalkanoic acids and shaped articles produced therefrom
WO1990001521A1 (en) Degradable thermoplastic from lactides
US20060009611A1 (en) Copolyetherester compositions containing hydroxyalkanoic acids and shaped articles produced therefrom
US7358325B2 (en) Sulfonated aromatic copolyesters containing hydroxyalkanoic acid groups and shaped articles produced therefrom
US20050151296A1 (en) Lactic acid-based resin composition
US20050203208A1 (en) Biologically and photochemically degradable polymeric compositions and film
US20050244606A1 (en) Biodegradable sheet, molded object obtained from the sheet, and process for producing the molded object

Legal Events

Date Code Title Description
AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM ZW

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
CFP Corrected version of a pamphlet front page
CR1 Correction of entry in section i
AK Designated states

Kind code of ref document: C1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: C1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase in:

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP